Semiconductor device and method for manufacturing the same

ABSTRACT

To reduce defects in an oxide semiconductor film in a semiconductor device. To improve the electrical characteristics and the reliability of a semiconductor device including an oxide semiconductor film. In a semiconductor device including a transistor including a gate electrode formed over a substrate, a gate insulating film covering the gate electrode, a multilayer film overlapping with the gate electrode with the gate insulating film provided therebetween, and a pair of electrodes in contact with the multilayer film, a first oxide insulating film covering the transistor, and a second oxide insulating film formed over the first oxide insulating film, the multilayer film includes an oxide semiconductor film and an oxide film containing In or Ga, the first oxide insulating film is an oxide insulating film through which oxygen is permeated, and the second oxide insulating film is an oxide insulating film containing more oxygen than that in the stoichiometric composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an object, a method, or a manufacturingmethod. Further, the present invention relates to a process, a machine,manufacture, or a composition of matter. In particular, the presentinvention relates to, for example, a semiconductor device, a displaydevice, a light-emitting device, a power storage device, a drivingmethod thereof, or a manufacturing method thereof. In particular, thepresent invention relates to, for example, a semiconductor deviceincluding an oxide semiconductor, a display device including an oxidesemiconductor, or a light-emitting device including an oxidesemiconductor. In particular, the present invention relates to, forexample, a semiconductor device including a transistor and a method formanufacturing the semiconductor device.

2. Description of the Related Art

Transistors used for most flat panel displays typified by a liquidcrystal display device and a light-emitting display device are formedusing silicon semiconductors such as amorphous silicon, single crystalsilicon, and polycrystalline silicon provided over glass substrates.Further, transistors formed using such silicon semiconductors are usedin integrated circuits (ICs) and the like.

In recent years, attention has been drawn to a technique in which,instead of a silicon semiconductor, a metal oxide exhibitingsemiconductor characteristics is used for transistors. Note that in thisspecification, a metal oxide exhibiting semiconductor characteristics isreferred to as an oxide semiconductor.

For example, a technique is disclosed in which a transistor ismanufactured using zinc oxide or an In—Ga—Zn-based oxide as an oxidesemiconductor and the transistor is used as a switching element or thelike of a pixel of a display device (see Patent Documents 1 and 2).

REFERENCE Patent Documents

-   [Patent Document 1] Japanese Published Patent Application No.    2007-123861-   [Patent Document 2] Japanese Published Patent Application No.    2007-96055

SUMMARY OF THE INVENTION

In a transistor using an oxide semiconductor film, a large number ofoxygen vacancies in the oxide semiconductor film cause poor electricalcharacteristics of the transistor and cause an increase in the amount ofchange in electrical characteristics of the transistor, typically thethreshold voltage due to a change over time or a stress test (e.g., abias-temperature (BT) stress test).

Thus, an object of one embodiment of the present invention is to reducedefects in an oxide semiconductor film of a semiconductor device or thelike including the oxide semiconductor film. Another object of oneembodiment of the present invention is to improve electricalcharacteristics of a semiconductor device or the like including an oxidesemiconductor film. Another object of one embodiment of the presentinvention is to improve reliability of a semiconductor device or thelike including an oxide semiconductor film. Another object of oneembodiment of the present invention is to provide a semiconductor deviceor the like with low off-state current. Another object of one embodimentof the present invention is to provide a semiconductor device or thelike with low power consumption. Another object of one embodiment of thepresent invention is to provide a display device or the like capable ofcausing less eyestrain. Another object of one embodiment of the presentinvention is to provide a semiconductor device or the like including atransparent semiconductor film. Another object of one embodiment of thepresent invention is to provide a novel semiconductor device or thelike. Another object of one embodiment of the present invention is toprovide a semiconductor device or the like having excellentcharacteristics. Note that the descriptions of these objects do notdisturb the existence of other objects. Note that in one embodiment ofthe present invention, there is no need to achieve all the objects. Notethat other objects will be apparent from the description of thespecification, the drawings, the claims, and the like and other objectscan be derived from the description of the specification, the drawings,the claims, and the like.

One embodiment of the present invention is a semiconductor deviceincluding a transistor including a gate electrode formed over asubstrate, a gate insulating film covering the gate electrode, amultilayer film overlapping with the gate electrode with the gateinsulating film provided therebetween, and a pair of electrodes incontact with the multilayer film, a first oxide insulating film coveringthe transistor, and a second oxide insulating film formed over the firstoxide insulating film. In the semiconductor device, the multilayer filmincludes an oxide semiconductor film and an oxide film containing In orGa, the first oxide insulating film is an oxide insulating film throughwhich oxygen is permeated, the second oxide insulating film is an oxideinsulating film containing more oxygen than that in the stoichiometriccomposition, and the transistor has characteristics in which, by abias-temperature stress test, threshold voltage does not change orchanges in a positive direction or a negative direction and the amountof the change in a negative direction or a positive direction is lessthan or equal to 1.0 V, preferably less than or equal to 0.5 V.

Note that the oxide semiconductor film preferably contains In or Ga.

Further, the energy of the conduction band bottom of the oxide filmcontaining In or Ga is closer to the vacuum level than the energy of theconduction band bottom of the oxide semiconductor film is. Furthermore,the difference between the energy of the conduction band bottom of theoxide film containing In or Ga and the energy of the conduction bandbottom of the oxide semiconductor film is preferably greater than orequal to 0.05 eV and less than or equal to 2 eV. Note that an energydifference between the vacuum level and the conduction band bottom isalso referred to as an electron affinity. Thus, it is preferable thatthe electron affinity of the oxide film containing In or Ga be less thanthe electron affinity of the oxide semiconductor film and the differencebe greater than or equal to 0.05 eV and less than or equal to 2 eV.

Further, it is preferable that each of the oxide semiconductor film andthe oxide film containing In or Ga be an In-M-Zn oxide (M represents Al,Ti, Ga, Y, Zr, La, Ce, Nd, or Hf) film and the proportion of M atoms inthe oxide film containing In or Ga be higher than that in the oxidesemiconductor film.

Further, it is preferable that, in the multilayer film, an absorptioncoefficient derived from a constant photocurrent method (CPM) be lowerthan 1×10⁻³/cm.

Further, it is preferable that the silicon concentration and the carbonconcentration between the oxide semiconductor film and the oxide filmcontaining In or Ga be lower than 2×10¹⁸ atoms/cm³.

Another embodiment of the present invention is a method formanufacturing a semiconductor device, including the steps of forming agate electrode and a gate insulating film, forming, over the gateinsulating film, a multilayer film including an oxide semiconductor filmand an oxide film containing In or Ga, forming a pair of electrodes incontact with the multilayer film, forming a first oxide insulating filmover the multilayer film and the pair of electrodes, and forming asecond oxide insulating film over the first oxide insulating film. Inthe method, a substrate placed in a treatment chamber which isvacuum-evacuated is held at a temperature higher than or equal to 180°C. and lower than or equal to 400° C., pressure in the treatment chamberis set to be greater than or equal to 20 Pa and less than or equal to250 Pa with introduction of a source gas into the treatment chamber, anda high-frequency power is supplied to an electrode provided in thetreatment chamber to form the first oxide insulating film. In addition,the substrate placed in a treatment chamber which is vacuum-evacuated isheld at a temperature higher than or equal to 180° C. and lower than orequal to 260° C., pressure in the treatment chamber is set to be greaterthan or equal to 100 Pa and less than or equal to 250 Pa withintroduction of a source gas into the treatment chamber, and ahigh-frequency power higher than or equal to 0.17 W/cm² and lower thanor equal to 0.5 W/cm² is supplied to the electrode provided in thetreatment chamber to form the second oxide insulating film.

In accordance with one embodiment of the present invention, defects inan oxide semiconductor film of a semiconductor device including theoxide semiconductor film can be reduced. Further, in accordance with oneembodiment of the present invention, the electrical characteristics of asemiconductor device including an oxide semiconductor film can beimproved. Further, in accordance with one embodiment of the presentinvention, reliability of a semiconductor device or the like includingan oxide semiconductor film can be improved. Further, in accordance withone embodiment of the present invention, a semiconductor device or thelike with low off-state current can be provided. Further, in accordancewith one embodiment of the present invention, a semiconductor device orthe like with low power consumption can be provided. Further, inaccordance with one embodiment of the present invention, a displaydevice or the like capable of causing less eyestrain can be provided.Further, in accordance with one embodiment of the present invention, asemiconductor device or the like including a transparent semiconductorfilm can be provided. Further, in accordance with one embodiment of thepresent invention, a novel semiconductor device or the like can beprovided. Further, in accordance with one embodiment of the presentinvention, a semiconductor device or the like having excellentcharacteristics can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1D are a top view and cross-sectional views illustrating oneembodiment of a transistor, and a graph illustrating Vg-Idcharacteristics of the transistor.

FIGS. 2A to 2C are diagrams illustrating the band structure of atransistor.

FIG. 3 is a cross-sectional view illustrating one embodiment of atransistor.

FIGS. 4A to 4D are cross-sectional views illustrating one embodiment ofa method for manufacturing a transistor.

FIGS. 5A to 5C are cross-sectional views each illustrating oneembodiment of a transistor.

FIGS. 6A to 6C are a top view and cross-sectional views illustrating oneembodiment of a transistor, and FIGS. 6D and 6E are cross-sectionalviews illustrating another embodiment of a transistor.

FIGS. 7A and 7B are diagrams illustrating the band structure of atransistor.

FIGS. 8A to 8C are a top view and cross-sectional views illustrating oneembodiment of a transistor.

FIGS. 9A to 9D are cross-sectional views illustrating one embodiment ofa method for manufacturing a transistor.

FIGS. 10A to 10C are a top view and cross-sectional views illustratingone embodiment of a transistor.

FIGS. 11A to 11D are cross-sectional views illustrating one embodimentof a method for manufacturing a transistor.

FIGS. 12A to 12C are a top view and cross-sectional views illustratingone embodiment of a transistor.

FIG. 13 is a cross-sectional view illustrating one embodiment of atransistor.

FIGS. 14A to 14C are top views each illustrating one embodiment of asemiconductor device.

FIGS. 15A and 15B are cross-sectional views each illustrating oneembodiment of a semiconductor device.

FIG. 16 is a top view illustrating one embodiment of a semiconductordevice.

FIG. 17 is a cross-sectional view illustrating one embodiment of asemiconductor device.

FIGS. 18A and 18B are diagrams illustrating one example of a connectionstructure of a common electrode of a display device and one example of aconnection structure of a wiring of a display device.

FIG. 19 is a cross-sectional view illustrating one embodiment of asemiconductor device.

FIG. 20 is a top view illustrating one embodiment of a semiconductordevice.

FIGS. 21A and 21B are a top view and a cross-sectional view illustratingone embodiment of a semiconductor device.

FIGS. 22A to 22C are an exploded perspective view and top views showingan example of a structure of a touch sensor.

FIGS. 23A and 23B are a cross-sectional view and a circuit diagramshowing an example of a structure of a touch sensor.

FIG. 24 is a block diagram showing an example of a structure of a liquidcrystal display device.

FIG. 25 is a timing chart illustrating one example of a method fordriving a liquid crystal display device.

FIGS. 26A to 26C are diagrams illustrating electronic devices eachincluding a semiconductor device which is one embodiment of the presentinvention.

FIGS. 27A to 27C are diagrams illustrating an electronic deviceincluding a semiconductor device which is one embodiment of the presentinvention.

FIGS. 28A to 28D are graphs showing the Vg-Id characteristics oftransistors.

FIG. 29 is a graph showing the amount of change in threshold voltage oftransistors after a BT photostress test.

FIGS. 30A to 30D are graphs each showing the Vg-Id characteristicsbefore and after a BT stress test.

FIG. 31 is a graph showing the amount of change in threshold voltage(ΔVth).

FIGS. 32A and 32B are graphs each showing the amount of change inthreshold voltage (ΔVth).

FIGS. 33A to 33C are graphs each showing the result of TDS measurement.

FIGS. 34A and 34B are graphs each showing the result of TDS measurement.

FIG. 35 is a graph illustrating the results of ESR measurement.

FIG. 36 is a graph illustrating the results of ESR measurement.

FIGS. 37A and 37B are graphs showing the results of CPM measurement of amultilayer film included in a transistor.

FIGS. 38A and 38B are graphs each showing the result of ToF-SIMS of amultilayer film included in a transistor.

FIGS. 39A and 39B are diagrams each illustrating the structure used incalculation of band structures.

FIG. 40 is a diagram illustrating the results of calculation of bandstructures.

FIGS. 41A to 41C are schematic views of oxide semiconductor films anddiagrams illustrating the band structures in the oxide semiconductorfilms.

FIG. 42 is a diagram illustrating the results of calculation of bandstructures.

FIG. 43 is a graph showing change of an energy barrier with respect to achannel length.

FIG. 44 is a schematic view of a display device.

FIG. 45 is a diagram showing the results of measuring current flowing intransistors.

FIG. 46 is a graph showing the results of measuring current flowing intransistors.

FIG. 47 is a photograph showing the results of display on displaydevices.

FIG. 48 is a diagram showing the results of measuring current flowing intransistors.

FIG. 49 is a diagram showing the results of measuring current flowing intransistors.

FIG. 50 is a diagram showing the results of measuring current flowing intransistors.

FIG. 51 is a diagram showing the results of measuring current flowing intransistors.

FIG. 52 is a graph showing the results of current stress tests oftransistors.

FIGS. 53A to 53F are graphs showing the results of SIMS measurement insamples.

FIGS. 54A and 54B are graphs showing the results of SIMS measurement insamples.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described in detail belowwith reference to the accompanying drawings. Note that the presentinvention is not limited to the following description and it is easilyunderstood by those skilled in the art that the mode and details can bevariously changed without departing from the scope and spirit of thepresent invention. Therefore, the present invention should not beconstrued as being limited to the description in the followingembodiments and examples. In addition, in the following embodiments andexamples, the same portions or portions having similar functions aredenoted by the same reference numerals or the same hatching patterns indifferent drawings, and description thereof will not be repeated.

Note that in each drawing described in this specification, the size, thefilm thickness, or the region of each structure is exaggerated forclarity in some cases and thus the actual scale is not necessarilylimited to the illustrated scale.

Note that terms such as “first”, “second”, and “third” in thisspecification are used in order to avoid confusion among components, andthe terms do not limit the components numerically. Therefore, forexample, the term “first” can be replaced with the term “second”,“third”, or the like as appropriate.

Functions of a “source” and a “drain” are sometimes replaced with eachother when the direction of current flow is changed in circuitoperation, for example. Therefore, the terms “source” and “drain” can beused to denote the drain and the source, respectively, in thisspecification.

Note that a voltage refers to a potential difference between two points,and a potential refers to electrostatic energy (electric potentialenergy) of unit charge at a given point in an electrostatic field. Notethat in general, a difference between a potential of one point and areference potential (e.g., a ground potential) is merely called apotential or a voltage, and a potential and a voltage are used assynonymous words in many cases. Thus, in this specification, a potentialmay be rephrased as a voltage and a voltage may be rephrased as apotential unless otherwise specified.

In this specification, in the case where an etching step is performedafter a photolithography process, a mask formed in the photolithographyprocess is removed after the etching step.

Embodiment 1

In this embodiment, a semiconductor device which is one embodiment ofthe present invention and a manufacturing method thereof are describedwith reference to drawings.

In a transistor including an oxide semiconductor film, oxygen vacanciesare given as an example of a defect which leads to poor electricalcharacteristics of the transistor. For example, the threshold voltage ofa transistor including an oxide semiconductor film which contains oxygenvacancies in the film easily shifts in the negative direction, and sucha transistor tends to have normally-on characteristics. This is becauseelectric charges are generated owing to oxygen vacancies in the oxidesemiconductor film and the resistance is thus reduced. The transistorhaving normally-on characteristics causes various problems in thatmalfunction is likely to be caused when in operation and that powerconsumption is increased when not in operation, for example. Further,there is a problem in that the amount of change in electricalcharacteristics, typically in threshold voltage, of the transistor isincreased by change over time or a stress test.

One of the factors in generating oxygen vacancies is damage caused in amanufacturing process of a transistor. For example, when an insulatingfilm or the like is formed over an oxide semiconductor film by a plasmaCVD method, the oxide semiconductor film might be damaged depending onformation conditions thereof.

Further, not only oxygen vacancies but also impurities such as siliconor carbon which is a constituent element of the insulating film causepoor electrical characteristics of a transistor. Therefore, there is aproblem in that mixing of the impurities into an oxide semiconductorfilm reduces the resistance of the oxide semiconductor film and theamount of change in electrical characteristics, typically in thresholdvoltage, of the transistor is increased by change over time or a stresstest.

Thus, an object of this embodiment is to reduce oxygen vacancies in anoxide semiconductor film having a channel region and the concentrationof impurities in the oxide semiconductor film, in a semiconductor deviceincluding a transistor having the oxide semiconductor film.

A top view and cross-sectional views of a transistor 50 included in asemiconductor device are shown in FIGS. 1A to 1C. FIG. 1A is a top viewof the transistor 50, FIG. 1B is a cross-sectional view taken alongdashed-dotted line A-B in FIG. 1A, and FIG. 1C is a cross-sectional viewtaken along dashed-dotted line C-D in FIG. 1A. Note that in FIG. 1A, asubstrate 11, a gate insulating film 17, an oxide insulating film 23, anoxide insulating film 24, a nitride insulating film 25, and the like areomitted for simplicity.

The transistor 50 shown in FIGS. 1B and 1C includes a gate electrode 15provided over the substrate 11. Further, the gate insulating film 17 isformed over the substrate 11 and the gate electrode 15, and a multilayerfilm 20 overlapping with the gate electrode 15 with the gate insulatingfilm 17 provided therebetween, and a pair of electrodes 21 and 22 incontact with the multilayer film 20 are included. Furthermore, aprotective film 26 including the oxide insulating film 23, the oxideinsulating film 24, and the nitride insulating film 25 is formed overthe gate insulating film 17, the multilayer film 20, and the pair ofelectrodes 21 and 22.

In the transistor 50 described in this embodiment, the multilayer film20 includes an oxide semiconductor film 18 and an oxide film 19containing In or Ga. Further, part of the oxide semiconductor film 18serves as a channel region. Furthermore, the oxide insulating film 23 isformed in contact with the multilayer film 20, and the oxide insulatingfilm 24 is formed in contact with the oxide insulating film 23. That is,the oxide film 19 containing In or Ga is provided between the oxidesemiconductor film 18 and the oxide insulating film 23.

The oxide semiconductor film 18 is typically In—Ga oxide film, In—Znoxide film, or In-M-Zn oxide film (M represents Al, Ti, Ga, Y, Zr, La,Ce, Nd, or Hf).

Note that when the oxide semiconductor film 18 is In-M-Zn oxide film,the atomic ratio of In to M is preferably as follows: the proportion ofIn atoms be higher than or equal to 25 atomic % and the proportion of Matoms be lower than 75 atomic %, and it is further preferably asfollows: the proportion of In atoms be higher than or equal to 34 atomic% and the proportion of M atoms be lower than 66 atomic %.

The energy gap of the oxide semiconductor film 18 is 2 eV or more,preferably 2.5 eV or more, more preferably 3 eV or more. With the use ofan oxide semiconductor having such a wide energy gap, the off-statecurrent of the transistor 50 can be reduced.

The thickness of the oxide semiconductor film 18 is greater than orequal to 3 nm and less than or equal to 200 nm, preferably greater thanor equal to 3 nm and less than or equal to 100 nm, more preferablygreater than or equal to 3 nm and less than or equal to 50 nm.

The oxide film 19 containing In or Ga is typically In—Ga oxide film,In—Zn oxide film, or In-M-Zn oxide film (M represents Al, Ti, Ga, Y, Zr,La, Ce, Nd, or Hf). The energy at the conduction band bottom thereof iscloser to a vacuum level than that of the oxide semiconductor film 18is, and typically, the difference between the energy at the conductionband bottom of the oxide film 19 containing In or Ga and the energy atthe conduction band bottom of the oxide semiconductor film 18 is any oneof 0.05 eV or more, 0.07 eV or more, 0.1 eV or more, and 0.15 eV ormore, and any one of 2 eV or less, 1 eV or less, 0.5 eV or less, and 0.4eV or less. That is, the difference between the electron affinity of theoxide film 19 containing In or Ga and the electron affinity of the oxidesemiconductor film 18 is any one of 0.05 eV or more, 0.07 eV or more,0.1 eV or more, and 0.15 eV or more, and any one of 2 eV or less, 1 eVor less, 0.5 eV or less, and 0.4 eV or less.

When the oxide film 19 containing In or Ga is In-M-Zn oxide film, theatomic ratio of In to M is preferably as follows: the proportion of Inatoms be lower than 50 atomic % and the proportion of M atoms be higherthan or equal to 50 atomic %, and it is further preferably as follows:the proportion of In atoms be lower than 25 atomic % and the proportionof M atoms be higher than or equal to 75 atomic %.

Further, in the case where each of the oxide semiconductor film 18 andthe oxide film 19 containing In or Ga is In-M-Zn oxide film (Mrepresents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf), the proportion of Matoms (M represents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf) in the oxidefilm 19 containing In or Ga is higher than that in the oxidesemiconductor film 18. Typically, the proportion of M in each of thefilms is 1.5 or more times, preferably twice or more, more preferablythree or more times as high as that in the oxide semiconductor film 18.

Furthermore, in the case where each of the oxide semiconductor film 18and the oxide film 19 containing In or Ga is In-M-Zn-based oxide film (Mrepresents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf), when In:M:Zn=x₁:y₁:z₁[atomic ratio] is satisfied in the oxide film 19 containing In or Ga andIn:M:Zn=x₂:y₂:z₂ [atomic ratio] is satisfied in the oxide semiconductorfilm 18, y₁/x₁ is higher than y₂/x₂. It is preferable that y₁/x₁ be 1.5or more times as high as y₂/x₂. It is further preferable that y₁/x₁ betwice or more as high as y₂/x₂. It is still further preferable thaty₁/x₁ be three or more times as high as y₂/x₂. In this case, it ispreferable that in the oxide semiconductor film, y₂ be higher than orequal to x₂ because a transistor including the oxide semiconductor filmcan have stable electric characteristics. However, when y₂ is largerthan or equal to three or more times x₂, the field-effect mobility ofthe transistor including the oxide semiconductor film is reduced. Thus,it is preferable that y₂ be lower than three times x₂.

In the case where the oxide semiconductor film 18 is In-M-Zn oxide film(M represents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf), it is preferablethat the atomic ratio of metal elements of a sputtering target used forforming a film of the In-M-Zn oxide film satisfy In≧M and Zn≧M. As theatomic ratio of metal elements of such a sputtering target,In:M:Zn=1:1:1 and In:M:Zn=3:1:2 are preferable. Further, in the casewhere the oxide film 19 containing In or Ga is In-M-Zn oxide film (Mrepresents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf), the atomic ratio ofmetal elements of a sputtering target used for forming a film of theIn-M-Zn oxide film preferably satisfies M>In and Zn>0.5×M, and morepreferably, Zn also satisfies Zn>M. As the atomic ratio of metalelements of such a sputtering target, In:Ga:Zn=1:3:2, In:Ga:Zn=1:3:4,In:Ga:Zn=1:3:5, In:Ga:Zn=1:3:6, In:Ga:Zn=1:3:7, In:Ga:Zn=1:3:8,In:Ga:Zn=1:3:9, In:Ga:Zn=1:3:10, In:Ga:Zn=1:6:4, In:Ga:Zn=1:6:5,In:Ga:Zn=1:6:6, In:Ga:Zn=1:6:7, In:Ga:Zn=1:6:8, In:Ga:Zn=1:6:9, andIn:Ga:Zn=1:6:10 are preferable. Note that the proportion of each metalelement in the atomic ratio of each of the oxide semiconductor film 18and the oxide film 19 containing In or Ga formed using theabove-described sputtering target varies within a range of ±20% as anerror.

An oxide semiconductor film with low carrier density is used for theoxide semiconductor film 18 and the oxide film 19 containing In or Ga.For example, an oxide semiconductor film whose carrier density is1×10¹⁷/cm³ or lower, preferably 1×10¹⁵/cm³ or lower, more preferably1×10¹³/cm³ or lower, much more preferably 1×10¹¹/cm³ or lower is usedfor the oxide semiconductor film 18 and the oxide film 19 containing Inor Ga.

Note that, without limitation to those described above, a material withan appropriate composition may be used depending on requiredsemiconductor characteristics and electrical characteristics (e.g.,field-effect mobility and threshold voltage) of a transistor. Further,in order to obtain required semiconductor characteristics of atransistor, it is preferable that the carrier density, the impurityconcentration, the defect density, the atomic ratio of a metal elementto oxygen, the interatomic distance, the density, and the like of theoxide semiconductor film 18 be set to be appropriate.

The oxide film 19 containing In or Ga also serves as a film whichrelieves damage to the oxide semiconductor film 18 at the time offorming the oxide insulating film 24 later.

The thickness of the oxide film 19 containing In or Ga is greater thanor equal to 3 nm and less than or equal to 100 nm, preferably greaterthan or equal to 3 nm and less than or equal to 50 nm.

When silicon or carbon, which is one of elements belonging to Group 14,is contained in the oxide semiconductor film 18, the number of oxygenvacancies is increased, and the oxide semiconductor film 18 becomes ann-type film. Thus, the concentration of silicon or carbon in the oxidesemiconductor film 18 or the concentration of silicon or carbon in thevicinity of an interface between the oxide film 19 containing In or Gaand the oxide semiconductor film 18 is adjusted to be lower than orequal to 2×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁷atoms/cm³.

Further, the crystal structure of each of the oxide semiconductor film18 and the oxide film 19 containing In or Ga may be an amorphousstructure, a single-crystal structure, a polycrystalline structure, or ac-axis aligned crystalline oxide semiconductor (CAAC-OS) which isdescribed later. Note that when the crystal structure of at least theoxide semiconductor film 18 is CAAC-OS, the amount of change inelectrical characteristics due to irradiation with visible light orultraviolet light can be further reduced.

Furthermore, in the transistor 50 described in this embodiment, theoxide insulating film 23 is formed in contact with the multilayer film20, and the oxide insulating film 24 in contact with the oxideinsulating film 23 is formed.

The oxide insulating film 23 is an oxide insulating film through whichoxygen is permeated. Note that the oxide insulating film 23 also servesas a film which relieves damage to the multilayer film 20 at the time offorming the oxide insulating film 24 later.

A silicon oxide film, a silicon oxynitride film, or the like with athickness greater than or equal to 5 nm and less than or equal to 150nm, preferably greater than or equal to 5 nm and less than or equal to50 nm can be used as the oxide insulating film 23. Note that in thisspecification, a “silicon oxynitride film” refers to a film thatincludes more oxygen than nitrogen, and a “silicon nitride oxide film”refers to a film that includes more nitrogen than oxygen.

Further, it is preferable that the number of defects in the oxideinsulating film 23 be small, typically the spin density of a signalwhich appears at g=2.001 due to a dangling bond of silicon, be lowerthan or equal to 3×10¹⁷ spins/cm³ by ESR measurement. This is because ifthe density of defects in the oxide insulating film 23 is high, oxygenis bonded to the defects and the amount of oxygen that passes throughthe oxide insulating film 23 is decreased.

Further, it is preferable that the number of defects at the interfacebetween the oxide insulating film 23 and the multilayer film 20 besmall, typically the spin density of a signal which appears at g=1.93due to a defect in the multilayer film 20 be lower than or equal to1×10¹⁷ spins/cm³, more preferably lower than or equal to the lower limitof detection by ESR measurement.

Note that in the oxide insulating film 23, all oxygen entering the oxideinsulating film 23 from the outside does not move to the outside of theoxide insulating film 23 and some oxygen remains in the oxide insulatingfilm 23. Further, movement of oxygen occurs in the oxide insulating film23 in some cases in such a manner that oxygen enters the oxideinsulating film 23 and oxygen contained in the oxide insulating film 23is moved to the outside of the oxide insulating film 23.

When the oxide insulating film through which oxygen is permeated isformed as the oxide insulating film 23, oxygen released from the oxideinsulating film 24 provided over the oxide insulating film 23 can bemoved to the oxide semiconductor film 18 through the oxide insulatingfilm 23.

The oxide insulating film 24 is formed in contact with the oxideinsulating film 23. The oxide insulating film 24 is an oxide insulatingfilm containing more oxygen than that in the stoichiometric composition.Part of oxygen is released by heating from the oxide insulating filmcontaining more oxygen than that in the stoichiometric composition. Theoxide insulating film containing more oxygen than that in thestoichiometric composition is an oxide insulating film of which theamount of released oxygen converted into oxygen atoms is greater than orequal to 1.0×10¹⁸ atoms/cm³, preferably greater than or equal to3.0×10²⁰ atoms/cm³ in TDS analysis.

A silicon oxide film, a silicon oxynitride film, or the like with athickness greater than or equal to 30 nm and less than or equal to 500nm, preferably greater than or equal to 50 nm and less than or equal to400 nm can be used as the oxide insulating film 24.

Further, it is preferable that the number of defects in the oxideinsulating film 24 be small, typically the spin density of a signalwhich appears at g=2.001 due to a dangling bond of silicon, be lowerthan 1.5×10¹⁸ spins/cm³, more preferably lower than or equal to 1×10¹⁸spins/cm³ by ESR measurement. Note that the oxide insulating film 24 isprovided more apart from the multilayer film 20 than the oxideinsulating film 23 is; thus, the oxide insulating film 24 may havehigher defect density than the oxide insulating film 23.

Here, the band structure along dashed-dotted line E-F in the vicinity ofthe multilayer film 20 of FIG. 1B is described with reference to FIG.2A, and the flow of carrier in the transistor 50 is described withreference to FIGS. 2B and 2C.

In the band structure shown in FIG. 2A, for example, In—Ga—Zn oxide (theatomic ratio of a sputtering target used for film formation isIn:Ga:Zn=1:1:1) with an energy gap of 3.15 eV is used for the oxidesemiconductor film 18. In—Ga—Zn oxide (the atomic ratio of a sputteringtarget used for film formation is In:Ga:Zn=1:3:2) with an energy gap of3.5 eV is used for the oxide film 19 containing In or Ga. Note that theenergy gap can be measured using a spectroscopic ellipsometer.

The energy difference between the vacuum level and the valence band top(also referred to as ionization potential) of the oxide semiconductorfilm 18 and the energy difference therebetween of the oxide film 19containing In or Ga are 7.9 eV and 8.0 eV, respectively. Note that theenergy difference between the vacuum level and the valence band top canbe measured using an ultraviolet photoelectron spectroscopy (UPS) device(VersaProbe manufactured by ULVAC-PHI, Inc.).

The energy difference between the vacuum level and the conduction bandbottom (also referred to as electron affinity) of the oxidesemiconductor film 18 and the energy difference therebetween of theoxide film 19 containing In or Ga are 4.7 eV and 4.5 eV, respectively.

Further, the conduction band bottom of the oxide semiconductor film 18is denoted by Ec_18, and the conduction band bottom of the oxide film 19containing In or Ga is denoted by Ec_19. Further, the conduction bandbottom of the gate insulating film 17 is denoted by Ec_17, and theconduction band bottom of the oxide insulating film 23 is denoted byEc_23.

As shown in FIG. 2A, in the multilayer film 20, the conduction bandbottom in the vicinity of the interface between the oxide semiconductorfilm 18 and the oxide film 19 containing In or Ga varies continuously.That is, there is no barrier in the vicinity of the interface betweenthe oxide semiconductor film 18 and the oxide film 19 containing In orGa, and the conduction band bottom smoothly varies. Such a shape iscaused by mutual transfer of oxygen between the oxide semiconductor film18 and the oxide film 19 containing In or Ga. Further, in the multilayerfilm 20, the energy of the conduction band bottom of the oxidesemiconductor film 18 is the lowest, and this region serves as a channelregion.

Now, a state where electrons serving as carrier flow in the transistoris described with reference to FIGS. 2B and 2C. Note that in FIGS. 2Band 2C, the number of electrons flowing in the oxide semiconductor film18 is represented by a size of a dotted arrow.

In the vicinity of the interface between the oxide film 19 containing Inor Ga and the oxide insulating film 23, trap states 27 are formed by animpurity and defects. Thus, for example, in the case where a channelregion of the transistor is formed with a single layer of the oxidesemiconductor film 18 as illustrated in FIG. 2B, in the oxidesemiconductor film 18, electrons serving as carrier flow mainly in thegate insulating film 17 side, but a small number of electrons also flowson the oxide insulating film 23 side. As a result, part of electronsflowing on the oxide semiconductor film 18 is captured by the trapstates 27.

On the other hand, in the transistor 50 described in this embodiment,the oxide film 19 containing In or Ga is provided between the oxidesemiconductor film 18 and the oxide insulating film 23 as illustrated inFIG. 2C; thus, there is a distance between the oxide semiconductor film18 and the trap states 27. As a result, electrons flowing in the oxidesemiconductor film 18 are less likely to be captured by the trap states27. When the electrons are captured by the trap states, the electronsbecome negative fixed charges. As a result, a threshold voltage of thetransistor fluctuates. However, by the distance between the oxidesemiconductor film 18 and the trap states 27, capture of the electronsby the trap states 27 can be reduced, and accordingly a fluctuation ofthe threshold voltage can be reduced.

Note that when the energy difference ΔE1 of the conduction band bottomin the vicinity of the interface between the oxide semiconductor film 18and the oxide film 19 containing In or Ga is small, carrier flowing inthe oxide semiconductor film 18 transcends the conduction band bottom ofthe oxide film 19 containing In or Ga and is captured by the trap states27. Thus, the energy difference ΔE1 between the conduction band bottomEc_18 of the oxide semiconductor film 18 and the conduction band bottomEc_19 of the oxide film 19 containing In or Ga is greater than or equalto 0.1 eV, preferably greater than or equal to 0.15 eV.

Further, the oxide insulating film 24 (see FIG. 1B) containing moreoxygen than that in the stoichiometric composition is provided on theback channel side of the multilayer film 20 (a surface of the multilayerfilm 20, which is opposite to a surface facing the gate electrode 15)with the oxide insulating film 23 through which oxygen is permeatedprovided therebetween. Therefore, oxygen contained in the oxideinsulating film 24 containing more oxygen than that in thestoichiometric composition is moved to the oxide semiconductor film 18included in the multilayer film 20, whereby oxygen vacancies in theoxide semiconductor film 18 can be reduced.

From the above, oxygen vacancies in the multilayer film 20 can bereduced by providing the multilayer film 20 including the oxidesemiconductor film 18 and the oxide film 19 containing In or Ga, and theoxide insulating film 24 containing more oxygen than that in thestoichiometric composition with the oxide insulating film 23 throughwhich oxygen is permeated provided therebetween, over the multilayerfilm 20. Further, by providing the oxide film 19 containing In or Gabetween the oxide semiconductor film 18 and the oxide insulating film23, the concentration of silicon or carbon in the oxide semiconductorfilm 18 or in the vicinity of the interface between the oxide film 19containing In or Ga and the oxide semiconductor film 18 can be reduced.Consequently, in the multilayer film 20, the absorption coefficientderived from a constant photocurrent method is lower than 1×10⁻³/cm,preferably lower than 1×10⁻⁴/cm. The absorption coefficient has apositive correlation with energy corresponding to the localized statesdue to oxygen vacancies and entry of impurities (calculated from awavelength); thus, the density of localized states in the multilayerfilm 20 is extremely low.

Note that the absorption coefficient which is called an Urbach tail dueto the band tail is removed from a curve of the absorption coefficientobtained by the CPM measurement, whereby the absorption coefficient dueto the localized states can be calculated from the following formula.Note that the Urbach tail indicates a constant gradient region on acurve of the absorption coefficient obtained by the CPM measurement, andthe gradient is called Urbach energy.

$\begin{matrix}{\int{\frac{{\alpha(E)} - \alpha_{u}}{E}{\mathbb{d}E}}} & \left\lbrack {{Formula}\mspace{14mu} 1} \right\rbrack\end{matrix}$

Here, α(E) indicates the absorption coefficient at each energy level andα_(u) indicates the absorption coefficient obtained by the Urbach tail.

Since the transistor 50 having such a structure includes very fewdefects in the multilayer film 20 including the oxide semiconductor film18, the electrical characteristics of the transistor can be improved.Further, due to a BT stress test and a BT photostress test which areexamples of a stress test, the threshold voltage does not change orchanges in the negative direction or the positive direction and theamount of the change is less than or equal to 1.0 V, preferably lessthan or equal to 0.5 V, and thus, reliability is high.

Here, electrical characteristics of a transistor having a small amountof change in threshold voltage in a BT stress test and a BT photostresstest are described with reference to FIG. 1D.

The BT stress test is one kind of accelerated test and can evaluate, ina short time, change in characteristics (i.e., change over time) oftransistors, which is caused by long-term use. In particular, the amountof change in threshold voltage of the transistor between before andafter the BT stress test is an important indicator when examining thereliability of the transistor. If the amount of change in the thresholdvoltage between before and after the BT stress test is small, thetransistor has higher reliability.

Next, a specific method of the BT stress test is described. First,initial characteristics of the transistor are measured. Next, thetemperature of the substrate over which the transistor is formed(substrate temperature) is set at fixed temperature, the pair ofelectrodes serving as a source and a drain of the transistor are set ata same potential, and the gate electrode is supplied for a certainperiod with potential different from that of the pair of electrodesserving as a source and a drain. The substrate temperature may bedetermined as appropriate in accordance with the test purpose. Then, thesubstrate temperature is set at a temperature similar to that of atemperature when the initial characteristics are measured, andelectrical characteristics of the transistor are measured again. As aresult, a difference between the threshold voltage in the initialcharacteristics and the threshold voltage after the BT stress test canbe obtained as the amount of change in the threshold voltage.

Note that the test in the case where the potential applied to the gateelectrode is higher than the potential of the source and the drain isreferred to as a positive BT stress test, and the test in the case wherethe potential applied to the gate electrode is lower than the potentialof the source and the drain is referred to as a negative BT stress test.A BT stress test with light irradiation is referred to as a BTphotostress test. The test in the case where light irradiation isperformed and the potential applied to the gate electrode is higher thanthe potential of the source and the drain is referred to as a positiveBT photostress test, and the test in the case where light irradiation isperformed and the potential applied to the gate electrode is lower thanthe potential of the source and the drain is referred to as a negativeBT photostress test.

The stress conditions for the BT stress test can be determined bysetting the substrate temperature, the electric field intensity appliedto the gate insulating film, and the time period of application of anelectric field. The intensity of the electric field applied to the gateinsulating film is determined in accordance with a value obtained bydividing a potential difference between the gate, and the source and thedrain by the thickness of the gate insulating film. For example, in thecase where the intensity of the electric field applied to a 100-nm-thickgate insulating film is to be 3 MV/cm, the potential difference betweenthe gate electrode, and the source and the drain can be set to 30 V.

FIG. 1D shows electrical characteristics of the transistor, and thehorizontal axis indicates the gate voltage (Vg) and the vertical axisindicates the drain current (Id). A dashed line 41 denotes the initialcharacteristics of the transistor, and a solid line 43 denotes theelectrical characteristics of the transistor after the BT stress test.In the transistor described in this embodiment, the amount of change inthreshold voltage in the dashed line 41 and the solid line 43 is 0 V orthe amount of change in the negative direction or the positive directionis less than or equal to 1.0 V, preferably less than or equal to 0.5 V.Therefore, in the transistor described in this embodiment, the thresholdvoltage changes little after the BT stress test. As a result, it isapparent that the transistor 50 described in this embodiment has highreliability.

Note that a transistor including an oxide semiconductor film is ann-channel transistor; therefore, in this specification, a transistorwhich can be regarded as having no drain current flowing therein when agate voltage is 0 V is defined as a transistor having normally-offcharacteristics. In contrast, a transistor which can be regarded ashaving a drain current flowing therein when a gate voltage is 0 V isdefined as a transistor having normally-on characteristics.

Further, in this specification, in a curve (not shown) where thehorizontal axis indicates the gate voltage (Vg [V]) and the verticalaxis indicates the square root of drain current (Id^(1/2) [A]), thethreshold voltage (Vth) is defined as a gate voltage at a point ofintersection of an extrapolated tangent line of Id^(1/2) having thehighest inclination with the Vg axis.

Other details of the transistor 50 are described below.

There is no particular limitation on a material and the like of thesubstrate 11 as long as the material has heat resistance high enough towithstand at least heat treatment performed later. For example, a glasssubstrate, a ceramic substrate, a quartz substrate, or a sapphiresubstrate may be used as the substrate 11. Alternatively, a singlecrystal semiconductor substrate or a polycrystalline semiconductorsubstrate made of silicon, silicon carbide, or the like, a compoundsemiconductor substrate made of silicon germanium or the like, an SOIsubstrate, or the like may be used. Still alternatively, any of thesesubstrates provided with a semiconductor element may be used as thesubstrate 11.

Alternatively, a flexible substrate may be used as the substrate 11, andthe transistor 50 may be provided directly on the flexible substrate.Alternatively, a separation layer may be provided between the substrate11 and the transistor 50. The separation layer can be used when part orthe whole of a semiconductor device formed over the separation layer iscompleted and separated from the substrate 11 and transferred to anothersubstrate. In such a case, the transistor 50 can be transferred to asubstrate having low heat resistance or a flexible substrate as well.

The gate electrode 15 can be formed using a metal element selected fromaluminum, chromium, copper, tantalum, titanium, molybdenum, andtungsten; an alloy containing any of these metal elements as acomponent; an alloy containing any of these metal elements incombination; or the like. Further, one or more metal elements selectedfrom manganese or zirconium may be used. The gate electrode 15 may havea single-layer structure or a stacked-layer structure of two or morelayers. For example, a single-layer structure of an aluminum filmcontaining silicon, a two-layer structure in which a titanium film isstacked over an aluminum film, a two-layer structure in which a titaniumfilm is stacked over a titanium nitride film, a two-layer structure inwhich a tungsten film is stacked over a titanium nitride film, atwo-layer structure in which a tungsten film is stacked over a tantalumnitride film or a tungsten nitride film, a three-layer structure inwhich a titanium film, an aluminum film, and a titanium film are stackedin this order, and the like can be given. Alternatively, an alloy filmor a nitride film in which aluminum and one or more elements selectedfrom titanium, tantalum, tungsten, molybdenum, chromium, neodymium, andscandium are combined may be used.

Further, the gate electrode 15 can be formed using a light-transmittingconductive material such as indium tin oxide, indium oxide containingtungsten oxide, indium zinc oxide containing tungsten oxide, indiumoxide containing titanium oxide, indium tin oxide containing titaniumoxide, indium zinc oxide, or indium tin oxide to which silicon oxide isadded. It is also possible to have a stacked-layer structure formedusing the above light-transmitting conductive material and the abovemetal element.

Further, an In—Ga—Zn-based oxynitride semiconductor film, an In—Sn-basedoxynitride semiconductor film, an In—Ga-based oxynitride semiconductorfilm, an In—Zn-based oxynitride semiconductor film, a Sn-basedoxynitride semiconductor film, an In-based oxynitride semiconductorfilm, a film of a metal nitride (such as InN or ZnN), or the like may beprovided between the gate electrode 15 and the gate insulating film 17.These films each have a work function higher than or equal to 5 eV,preferably higher than or equal to 5.5 eV, which is higher than theelectron affinity of an oxide semiconductor; thus, the threshold voltageof a transistor including the oxide semiconductor can be shifted in thepositive direction, and accordingly, a switching element having what iscalled normally-off characteristics can be obtained. For example, in thecase of using an In—Ga—Zn-based oxynitride semiconductor film, anIn—Ga—Zn-based oxynitride semiconductor film having a higher nitrogenconcentration than at least the oxide semiconductor film 18,specifically, an In—Ga—Zn-based oxynitride semiconductor film having anitrogen concentration of higher than or equal to 7 atomic % is used.

The gate insulating film 17 can be formed to have a single-layerstructure or a stacked-layer structure using, for example, any ofsilicon oxide, silicon oxynitride, silicon nitride oxide, siliconnitride, aluminum oxide, hafnium oxide, gallium oxide, Ga—Zn-based metaloxide, and silicon nitride. Further, as shown in FIG. 3, the gateinsulating film 17 can be formed to have a stacked-layer structure of agate insulating film 17 a and a gate insulating film 17 b, and an oxideinsulating film from which oxygen is released by heating may be used forthe gate insulating film 17 b in contact with the multilayer film 20.With the use of a film from which oxygen is released by heating as thegate insulating film 17 b, density of interface states at the interfacebetween the oxide semiconductor film 18 and the gate insulating film 17can be reduced; accordingly, a transistor with less deterioration inelectrical characteristics can be obtained. Further, it is possible toprevent outward diffusion of oxygen from the oxide semiconductor film 18and entry of hydrogen, water, or the like into the oxide semiconductorfilm 18 from the outside by providing an insulating film having ablocking effect against oxygen, hydrogen, water, and the like as thegate insulating film 17 a. The insulating film having a blocking effectagainst oxygen, hydrogen, water, and the like is formed using aluminumoxide, aluminum oxynitride, gallium oxide, gallium oxynitride, yttriumoxide, yttrium oxynitride, hafnium oxide, hafnium oxynitride, or thelike.

The gate insulating film 17 may be formed using a high-k material suchas hafnium silicate (HfSiO_(x)), hafnium silicate to which nitrogen isadded (HfSi_(x)O_(y)N_(z)), hafnium aluminate to which nitrogen is added(HfAl_(x)O_(y)N_(z)), hafnium oxide, or yttrium oxide, so that gateleakage current of the transistor can be reduced.

The thickness of the gate insulating film 17 may be greater than orequal to 5 nm and less than or equal to 400 nm, preferably greater thanor equal to 10 nm and less than or equal to 300 nm, more preferablygreater than or equal to 50 nm and less than or equal to 250 nm.

The pair of electrodes 21 and 22 is formed to have a single-layerstructure or a stacked-layer structure including, as a conductivematerial, any of metals such as aluminum, titanium, chromium, nickel,copper, yttrium, zirconium, molybdenum, silver, tantalum, and tungstenor an alloy containing any of these metals as its main component. Forexample, a single-layer structure of an aluminum film containingsilicon, a two-layer structure in which a titanium film is stacked overan aluminum film, a two-layer structure in which a titanium film isstacked over a tungsten film, a two-layer structure in which a copperfilm is formed over a copper-magnesium-aluminum alloy film, athree-layer structure in which a titanium film or a titanium nitridefilm, an aluminum film or a copper film, and a titanium film or atitanium nitride film are stacked in this order, a three-layer structurein which a molybdenum film or a molybdenum nitride film, an aluminumfilm or a copper film, and a molybdenum film or a molybdenum nitridefilm are stacked in this order, and the like can be given. Note that atransparent conductive material containing indium oxide, tin oxide, orzinc oxide may be used.

Further, it is possible to prevent outward diffusion of oxygen from themultilayer film 20 and entry of hydrogen, water, or the like into themultilayer film 20 from the outside by providing the nitride insulatingfilm 25 having a blocking effect against oxygen, hydrogen, water, andthe like over the oxide insulating film 24. The nitride insulating filmis formed using silicon nitride, silicon nitride oxide, aluminumnitride, aluminum nitride oxide, or the like. Note that instead of thenitride insulating film having a blocking effect against oxygen,hydrogen, water, and the like, an oxide insulating film having ablocking effect against oxygen, hydrogen, water, and the like, may beprovided. As the oxide insulating film having a blocking effect againstoxygen, hydrogen, water, and the like, an aluminum oxide film, analuminum oxynitride film, a gallium oxide film, a gallium oxynitridefilm, an yttrium oxide film, an yttrium oxynitride film, a hafnium oxidefilm, and a hafnium oxynitride film can be given.

Next, a method for manufacturing the transistor 50 shown in FIGS. 1A to1D is described with reference to FIGS. 4A to 4D.

As shown in FIG. 4A, the gate electrode 15 is formed over the substrate11, and the gate insulating film 17 is formed over the gate electrode15.

Here, a glass substrate is used as the substrate 11.

A method for forming the gate electrode 15 is described below. First, aconductive film is formed by a sputtering method, a CVD method, anevaporation method, or the like, and a mask is formed over theconductive film by a photolithography process. Next, part of theconductive film is etched with the use of the mask to form the gateelectrode 15. After that, the mask is removed.

Note that the gate electrode 15 may be formed by an electrolytic platingmethod, a printing method, an inkjet method, or the like instead of theabove formation method.

Here, a 100-nm-thick tungsten film is formed by a sputtering method.Next, a mask is formed by a photolithography process, and the tungstenfilm is subjected to dry etching with the use of the mask to form thegate electrode 15.

The gate insulating film 17 is formed by a sputtering method, a CVDmethod, an evaporation method, or the like.

In the case where a silicon oxide film, a silicon oxynitride film, or asilicon nitride oxide film is formed as the gate insulating film 17, adeposition gas containing silicon and an oxidizing gas are preferred tobe used as source gases. Typical examples of the deposition gascontaining silicon include silane, disilane, trisilane, and silanefluoride. As the oxidizing gas, oxygen, ozone, dinitrogen monoxide,nitrogen dioxide, and the like can be given as examples.

In the case where a silicon nitride film is formed as the gateinsulating film 17, it is preferable to use a two-step formation method.First, a first silicon nitride film with few defects is formed by aplasma CVD method in which a mixed gas of silane, nitrogen, and ammoniais used as a source gas. Then, a second silicon nitride film which has alow hydrogen concentration and is capable of blocking hydrogen is formedby switching the source gas to a mixed gas of silane and nitrogen. Withsuch a formation method, a silicon nitride film with few defects and ablocking property against hydrogen can be formed as the gate insulatingfilm 17.

Moreover, in the case of forming a gallium oxide film as the gateinsulating film 17, a metal organic chemical vapor deposition (MOCVD)method can be employed.

Next, as shown in FIG. 4B, the oxide semiconductor film 18 and the oxidefilm 19 containing In or Ga are formed over the gate insulating film 17.

Methods for forming the oxide semiconductor film 18 and the oxide film19 containing In or Ga are described below. An oxide semiconductor filmwhich is to be the oxide semiconductor film 18 and an oxide filmcontaining In or Ga which is to be the oxide film 19 containing In or Gaare successively formed over the gate insulating film 17. Next, after amask is formed over the oxide film containing In or Ga by aphotolithography process, the oxide semiconductor film and the oxidefilm containing In or Ga are partly etched with the use of the mask;thus, as shown in FIG. 4B, the multilayer film 20 which is subjected toelement isolation and includes the oxide semiconductor film 18 and theoxide film 19 containing In or Ga is formed over the gate insulatingfilm 17 so as to overlap with part of the gate electrode 15. After that,the mask is removed.

The oxide semiconductor film which is to be the oxide semiconductor film18 and the oxide film containing In or Ga which is to be the oxide film19 containing In or Ga can be formed by a sputtering method, a coatingmethod, a pulsed laser deposition method, a laser ablation method, orthe like.

In the case where the oxide semiconductor film and the oxide filmcontaining In or Ga are formed by a sputtering method, an RF powersupply device, an AC power supply device, a DC power supply device, orthe like can be used as appropriate as a power supply device forgenerating plasma.

As a sputtering gas, a rare gas (typically argon), an oxygen gas, or amixed gas of a rare gas and oxygen is used as appropriate. In the caseof using the mixed gas of a rare gas and oxygen, the proportion ofoxygen is preferably higher than that of a rare gas.

Further, a target may be selected as appropriate in accordance with thecomposition of the oxide semiconductor film and the oxide filmcontaining In or Ga to be formed.

Note that, for example, when a sputtering method is used to form theoxide semiconductor film and the oxide film containing In or Ga, theoxide semiconductor film and the oxide film containing In or Ga areformed while heating at a substrate temperature higher than or equal to150° C. and lower than or equal to 500° C., preferably higher than orequal to 150° C. and lower than or equal to 450° C., more preferablyhigher than or equal to 200° C. and lower than or equal to 350° C.,whereby a CAAC-OS film which is described later can be formed.

The oxide semiconductor film and the oxide film containing In or Ga arenot simply stacked but formed to have a continuous energy band (to havea structure in which the energy at the bottom of the conduction bandvaries continuously across the films). In other words, a stacked-layerstructure in which an impurity which forms a defect state such as a trapcenter or a recombination center or a barrier blocking the flow ofcarrier does not exist at the interface between the films is formed. Ifan impurity exists between the oxide semiconductor film and the oxidefilm containing In or Ga which are stacked, a continuity of the energyband is damaged, and the carrier is captured or recombined at theinterface and then disappears.

In order to form such a continuous energy band, it is necessary to formfilms continuously without being exposed to air, with use of amulti-chamber deposition apparatus (sputtering apparatus) including aload lock chamber. Each chamber in the sputtering apparatus ispreferably evacuated to be a high vacuum state (to the degree of about1×10⁻⁴ Pa to 5×10⁻⁷ Pa) with an adsorption vacuum evacuation pump suchas a cryopump in order to remove water or the like, which serves as animpurity against the oxide semiconductor film, as much as possible.Alternatively, a turbo molecular pump and a cold trap are preferablycombined so as to prevent a backflow of a gas, especially a gascontaining carbon or hydrogen from an exhaust system to the inside ofthe chamber.

In order to obtain a highly purified intrinsic oxide semiconductor film,besides the high vacuum evacuation of the chamber, a highly purificationof a sputtering gas is also needed. As an oxygen gas or an argon gasused for a sputtering gas, a gas which is highly purified to have a dewpoint of −40° C. or lower, preferably −80° C. or lower, furtherpreferably −100° C. or lower, still further preferably −120° C. or loweris used, whereby entry of moisture or the like into the oxidesemiconductor film can be prevented as much as possible.

Here, a 35-nm-thick In—Ga—Zn oxide film (the atomic ratio of asputtering target used for film formation is In:Ga:Zn=1:1:1) is formedas the oxide semiconductor film by a sputtering method, and then, a20-nm-thick In—Ga—Zn oxide film (the atomic ratio of a sputtering targetused for film formation is In:Ga:Zn=1:3:2) is formed as the oxide filmcontaining In or Ga by a sputtering method. Next, a mask is formed overthe oxide film containing In or Ga, and the oxide semiconductor film andthe oxide film containing In or Ga are partly and selectively etched toform the multilayer film 20 including the oxide semiconductor film 18and the oxide film 19 containing In or Ga.

After that, heat treatment may be performed.

Next, as shown in FIG. 4C, the pair of electrodes 21 and 22 is formed.

A method for forming the pair of electrodes 21 and 22 is describedbelow. First, a conductive film is formed by a sputtering method, a CVDmethod, an evaporation method, or the like. Then, a mask is formed overthe conductive film by a photolithography process. Next, the conductivefilm is etched with the use of the mask to form the pair of electrodes21 and 22. After that, the mask is removed.

Here, a 50-nm-thick tungsten film, a 400-nm-thick aluminum film, and a100-nm-thick titanium film are sequentially stacked by a sputteringmethod. Next, a mask is formed over the titanium film by aphotolithography process and the tungsten film, the aluminum film, andthe titanium film are dry-etched with use of the mask to form the pairof electrodes 21 and 22.

Next, as shown in FIG. 4D, the oxide insulating film 23 is formed overthe multilayer film 20 and the pair of electrodes 21 and 22. Next, theoxide insulating film 24 is formed over the oxide insulating film 23.

Note that after the oxide insulating film 23 is formed, the oxideinsulating film 24 is preferably formed in succession without exposureto the air. After the oxide insulating film 23 is formed, the oxideinsulating film 24 is formed in succession by adjusting at least one ofthe flow rate of a source gas, pressure, a high-frequency power, and asubstrate temperature without exposure to the air, whereby theconcentration of impurities attributed to the atmospheric component atthe interface between the oxide insulating film 23 and the oxideinsulating film 24 can be reduced and oxygen in the oxide insulatingfilm 24 can be moved to the oxide semiconductor film 18; accordingly,the number of oxygen vacancies in the oxide semiconductor film 18 can bereduced.

As for the oxide insulating film 23, a silicon oxide film or a siliconoxynitride film can be formed as the oxide insulating film 23 under thefollowing conditions: the substrate placed in a treatment chamber of aplasma CVD apparatus, which is vacuum-evacuated, is held at atemperature higher than or equal to 180° C. and lower than or equal to400° C., preferably higher than or equal to 200° C. and lower than orequal to 370° C., the pressure is greater than or equal to 20 Pa andless than or equal to 250 Pa, preferably greater than or equal to 20 Paand less than 100 Pa or preferably greater than or equal to 100 Pa andless than or equal to 250 Pa with introduction of source gases into thetreatment chamber, and a high-frequency power is supplied to anelectrode provided in the treatment chamber.

A deposition gas containing silicon and an oxidizing gas are preferablyused as the source gases of the oxide insulating film 23. Typicalexamples of the deposition gas containing silicon include silane,disilane, trisilane, and silane fluoride. As the oxidizing gas, oxygen,ozone, dinitrogen monoxide, nitrogen dioxide, and the like can be givenas examples.

With the use of the above conditions, an oxide insulating film throughwhich oxygen is permeated can be formed as the oxide insulating film 23.Further, by providing the oxide film 19 containing In or Ga and theoxide insulating film 23, damage to the oxide semiconductor film 18 canbe reduced in a step of forming the oxide insulating film 24 which isformed later. Note that by setting the pressure in the treatment chamberto be greater than or equal to 100 Pa and less than or equal to 250 Pa,the amount of water contained in the oxide insulating film 23 isreduced; thus, variation in electrical characteristics of the transistor50 can be reduced and change in threshold voltage can be inhibited.Further, by setting the pressure in the treatment chamber to be greaterthan or equal to 100 Pa and less than or equal to 250 Pa, damage to themultilayer film 20 including the oxide semiconductor film 18 can bereduced when the oxide insulating film 23 is formed, so that the numberof oxygen vacancies contained in the oxide semiconductor film 18 can bereduced. In particular, when the film formation temperature of the oxideinsulating film 23 or the oxide insulating film 24 which is formed lateris set to be high, typically higher than 220° C., part of oxygencontained in the oxide semiconductor film 18 is released and oxygenvacancies are easily formed. Further, when the film formation conditionsfor reducing the number of defects in the oxide insulating film 24 whichis formed later are used to increase reliability of the transistor, theamount of released oxygen is easily reduced. Thus, it is difficult toreduce oxygen vacancies in the oxide semiconductor film 18 in somecases. However, by setting the pressure in the treatment chamber to begreater than or equal to 100 Pa and less than or equal to 250 Pa toreduce damage to the oxide semiconductor film 18 at the time of formingthe oxide insulating film 23, oxygen vacancies in the oxidesemiconductor film 18 can be reduced even when the amount of oxygenreleased from the oxide insulating film 24 is small.

Note that when the ratio of the amount of the oxidizing gas to theamount of the deposition gas containing silicon is 100 or higher, thehydrogen content in the oxide insulating film 23 can be reduced.Consequently, the amount of hydrogen entering the oxide semiconductorfilm 18 can be reduced; thus, the negative shift in the thresholdvoltage of the transistor can be inhibited.

Further, as the oxide insulating film 23, a silicon oxide film or asilicon oxynitride film can be formed under the following conditions:the substrate placed in the treatment chamber of the plasma CVDapparatus, which is vacuum-evacuated, is held at a temperature higherthan or equal to 300° C. and lower than or equal to 400° C., preferablyhigher than or equal to 320° C. and lower than or equal to 370° C.; thepressure is greater than or equal to 20 Pa and less than or equal to 250Pa with introduction of the source gases into the treatment chamber; anda high-frequency power is supplied to an electrode provided in thetreatment chamber.

In the above film formation conditions, when the substrate temperatureis set to the above-described temperature, the bonding strength ofsilicon and oxygen becomes high. Thus, as the oxide insulating film 23,a dense and hard oxide insulating film through which oxygen ispermeated, typically, a silicon oxide film or a silicon oxynitride filmof which etching using hydrofluoric acid of 0.5 wt % at 25° C. isperformed at a rate of lower than or equal to 10 nm/min, preferablylower than or equal to 8 nm/min can be formed.

Here, as the oxide insulating film 23, a 50-nm-thick silicon oxynitridefilm is formed by a plasma CVD method in which silane with a flow rateof 30 sccm and dinitrogen monoxide with a flow rate of 4000 sccm areused as source gases, the pressure in the treatment chamber is 200 Pa,the substrate temperature is 220° C., and a high-frequency power of 150W is supplied to parallel plate electrodes with the use of a 27.12 MHzhigh-frequency power source. Under such conditions, a silicon oxynitridefilm through which oxygen is permeated can be formed.

As the oxide insulating film 24, a silicon oxide film or a siliconoxynitride film is formed under the following conditions: the substrateplaced in the treatment chamber of the plasma CVD apparatus, which isvacuum-evacuated, is held at a temperature higher than or equal to 180°C. and lower than or equal to 260° C., preferably higher than or equalto 200° C. and lower than or equal to 240° C., the pressure is greaterthan or equal to 100 Pa and less than or equal to 250 Pa, preferablygreater than or equal to 100 Pa and less than or equal to 200 Pa withintroduction of source gases into the treatment chamber, and ahigh-frequency power of greater than or equal to 0.17 W/cm² and lessthan or equal to 0.5 W/cm², preferably greater than or equal to 0.25W/cm² and less than or equal to 0.35 W/cm² is supplied to the electrodeprovided in the treatment chamber.

A deposition gas containing silicon and an oxidizing gas are preferablyused as the source gases of the oxide insulating film 24. Typicalexamples of the deposition gas containing silicon include silane,disilane, trisilane, and silane fluoride. As the oxidizing gas, oxygen,ozone, dinitrogen monoxide, nitrogen dioxide, and the like can be given.

As the film formation conditions of the oxide insulating film 24, thehigh-frequency power having the above power density is supplied to thetreatment chamber having the above pressure, whereby the degradationefficiency of the source gas in plasma is increased, oxygen radicals areincreased, and oxidation of the source gas is promoted; therefore, theoxygen content in the oxide insulating film 24 becomes higher than thatin the stoichiometric composition. However, in the case where thesubstrate temperature is the above-described temperature, the bondingstrength between silicon and oxygen is low, and accordingly, part ofoxygen is released by heating. Thus, it is possible to form an oxideinsulating film which contains more oxygen than that in thestoichiometric composition and from which part of oxygen is released byheating. Further, the oxide insulating film 23 is provided over themultilayer film 20. Thus, during a step of forming the oxide insulatingfilm 24, the oxide insulating film 23 serves as a protective film of themultilayer film 20. Further, the oxide film 19 containing In or Gaserves as a protective film of the oxide semiconductor film 18.Consequently, the oxide insulating film 24 can be formed using thehigh-frequency power having a high power density while damage to theoxide semiconductor film 18 is reduced.

Note that in the film formation conditions of the oxide insulating film24, the flow rate of the deposition gas containing silicon relative tothe oxidizing gas can be increased, whereby the number of defects in theoxide insulating film 24 can be reduced. Typically, it is possible toform an oxide insulating film in which the number of defects is small,i.e. the spin density of a signal which appears at g=2.001 due to adangling bond of silicon, be lower than 6×10¹⁷ spins/cm³, preferablylower than or equal to 3×10¹⁷ spins/cm³, more preferably lower than orequal to 1.5×10¹⁷ spins/cm³ by ESR measurement. As a result, thereliability of the transistor can be improved.

Here, as the oxide insulating film 24, a 400-nm-thick silicon oxynitridefilm is formed by a plasma CVD method in which silane with a flow rateof 200 sccm and dinitrogen monoxide with a flow rate of 4000 sccm areused as the source gases, the pressure in the treatment chamber is 200Pa, the substrate temperature is 220° C., and the high-frequency powerof 1500 W is supplied to the parallel plate electrodes with the use of a27.12 MHz high-frequency power source. Note that the plasma CVDapparatus is a parallel plate plasma CVD apparatus in which theelectrode area is 6000 cm², and the power per unit area (power density)into which the supplied power is converted is 0.25 W/cm².

Next, heat treatment is performed. The temperature of the heat treatmentis typically higher than or equal to 150° C. and lower than the strainpoint of the substrate, preferably higher than or equal to 200° C. andlower than or equal to 450° C., more preferably higher than or equal to300° C. and lower than or equal to 450° C.

An electric furnace, an RTA apparatus, or the like can be used for theheat treatment. With the use of an RTA apparatus, the heat treatment canbe performed at a temperature of higher than or equal to the strainpoint of the substrate if the heating time is short. Therefore, the heattreatment time can be shortened.

The heat treatment may be performed under an atmosphere of nitrogen,oxygen, ultra-dry air (air in which a water content is 20 ppm or less,preferably 1 ppm or less, more preferably 10 ppb or less), or a rare gas(argon, helium, or the like). Note that the nitrogen, the oxygen, theultra-dry air, or the rare gas preferably does not contain hydrogen,water, and the like.

By the heat treatment, part of oxygen contained in the oxide insulatingfilm 24 can be moved to the oxide semiconductor film 18, so that thenumber of oxygen vacancies contained in the oxide semiconductor film 18can be reduced.

Further, in the case where water, hydrogen, or the like is contained inthe oxide insulating film 23 and the oxide insulating film 24, when thenitride insulating film 25 having a function of blocking water,hydrogen, and the like is formed later and heat treatment is performed,water, hydrogen, or the like contained in the oxide insulating film 23and the oxide insulating film 24 are moved to the oxide semiconductorfilm 18, so that defects are generated in the oxide semiconductor film18. However, by the heating, water, hydrogen, or the like contained inthe oxide insulating film 23 and the oxide insulating film 24 can bereleased; thus, variation in electrical characteristics of thetransistor 50 can be reduced, and change in threshold voltage can beinhibited.

Note that the oxide insulating film 24 can be formed over the oxideinsulating film 23 while heating, whereby oxygen can be moved to theoxide semiconductor film 18 and oxygen vacancies contained in the oxidesemiconductor film 18 can be reduced accordingly. Therefore, the heattreatment is not necessarily performed.

Here, the heat treatment is performed at 350° C. in an atmosphere ofnitrogen and oxygen for one hour.

Further, when the pair of electrodes 21 and 22 is formed, the multilayerfilm 20 is damaged by etching of the conductive film, so that oxygenvacancies are generated on the back-channel side of the multilayer film20. However, with the use of the oxide insulating film containing moreoxygen than that in the stoichiometric composition as the oxideinsulating film 24, the oxygen vacancies generated on the back channelside can be repaired by heat treatment. By this, defects contained inthe multilayer film 20 can be reduced, and thus, the reliability of thetransistor 50 can be improved.

Next, the nitride insulating film 25 is formed by a sputtering method, aCVD method, or the like.

Note that in the case where the nitride insulating film 25 is formed bya plasma CVD method, the substrate placed in the treatment chamber ofthe plasma CVD apparatus, which is vacuum-evacuated, is preferably setto be higher than or equal to 300° C. and lower than or equal to 400°C., more preferably, higher than or equal to 320° C. and lower than orequal to 370° C., so that a dense nitride insulating film can be formed.

In the case where a silicon nitride film is formed by the plasma CVDmethod as the nitride insulating film 25, a deposition gas containingsilicon, nitrogen, and ammonia is preferably used as a source gas. Asthe source gas, a small amount of ammonia compared to the amount ofnitrogen is used, whereby ammonia is dissociated in the plasma andactivated species are generated. The activated species cleave a bondbetween silicon and hydrogen which are contained in a deposition gascontaining silicon and a triple bond between nitrogen molecules. As aresult, a dense silicon nitride film having few defects, in which a bondbetween silicon and nitrogen is promoted and a bond between silicon andhydrogen is few can be formed. On the other hand, when the amount ofammonia with respect to nitrogen is large in the source gas, cleavage ofa deposition gas containing silicon and cleavage of nitrogen are notpromoted, so that a sparse silicon nitride film in which a bond betweensilicon and hydrogen remains and defects are increased is formed.Therefore, in the source gas, a flow rate ratio of the nitrogen to theammonia is set to be greater than or equal to 5 and less than or equalto 50, preferably greater than or equal to 10 and less than or equal to50.

Here, in the treatment chamber of a plasma CVD apparatus, a 50-nm-thicksilicon nitride film is formed by a plasma CVD method in which silanewith a flow rate of 50 sccm, nitrogen with a flow rate of 5000 sccm, andammonia with a flow rate of 100 sccm are used as the source gas, thepressure in the treatment chamber is 100 Pa, the substrate temperatureis 350° C., and high-frequency power of 1000 W is supplied toparallel-plate electrodes with a high-frequency power supply of 27.12MHz. Note that the plasma CVD apparatus is a parallel-plate plasma CVDapparatus in which the electrode area is 6000 cm², and the power perunit area (power density) into which the supplied power is converted is1.7×10⁻¹ W/cm².

By the above-described steps, the protective film 26 including the oxideinsulating film 23, the oxide insulating film 24, and the nitrideinsulating film 25 can be formed.

Next, heat treatment may be performed. The temperature of the heattreatment is typically higher than or equal to 150° C. and lower thanthe strain point of the substrate, preferably higher than or equal to200° C. and lower than or equal to 450° C., more preferably higher thanor equal to 300° C. and lower than or equal to 450° C.

By the above-described process, the transistor 50 can be manufactured.

The oxide insulating film containing more oxygen than that in thestoichiometric composition is formed to overlap with the oxidesemiconductor film which serves as a channel region, and thus, oxygen inthe oxide insulating film can be moved to the oxide semiconductor film.Consequently, the number of oxygen vacancies in the oxide semiconductorfilm can be reduced.

In particular, the oxide insulating film through which oxygen ispermeated is formed between the oxide semiconductor film which serves asa channel region and the oxide insulating film containing more oxygenthan that in the stoichiometric composition. Thus, damage to the oxidesemiconductor film at the time of forming the oxide insulating filmcontaining more oxygen than that in the stoichiometric composition canbe reduced. Consequently, the number of oxygen vacancies in the oxidesemiconductor film can be reduced.

Further, the oxide film containing In or Ga is formed over the oxidesemiconductor film, whereby damage to the oxide semiconductor film atthe time of forming the oxide insulating film containing more oxygenthan that in the stoichiometric composition can be further reduced. Inaddition, by forming the oxide film containing In or Ga, mixing of aconstituent element of an insulating film, e.g., the oxide insulatingfilm, formed over the oxide semiconductor film to the oxidesemiconductor film can be inhibited.

From the above, a semiconductor device including an oxide semiconductorfilm, in which the number of defects is reduced, can be obtained.Further, a semiconductor device including an oxide semiconductor filmand having improved electrical characteristics can be obtained.

Modification Example 1

In the transistor 50 described in this embodiment, a base insulatingfilm may be provided between the substrate 11 and the gate electrode 15as necessary. As a material of the base insulating film, silicon oxide,silicon oxynitride, silicon nitride, silicon nitride oxide, galliumoxide, hafnium oxide, yttrium oxide, aluminum oxide, aluminumoxynitride, and the like can be given as examples. Note that whensilicon nitride, gallium oxide, hafnium oxide, yttrium oxide, aluminumoxide, or the like is used as a material of the base insulating film, itis possible to inhibit diffusion of impurities such as alkali metal,water, and hydrogen into the multilayer film 20 from the substrate 11.

The base insulating film can be formed by a sputtering method, a CVDmethod, or the like.

Modification Example 2

It is preferable to use, as the oxide semiconductor film 18 provided inthe transistor 50 described in this embodiment, an oxide semiconductorfilm in which the impurity concentration is low and density of defectstates is low, in which case a transistor with more excellent electricalcharacteristics can be manufactured. Here, the state in which impurityconcentration is low and density of defect states is low (the number ofoxygen vacancies is small) is referred to as “highly purified intrinsic”or “substantially highly purified intrinsic”. A highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorhas few carrier generation sources, and thus has a low carrier densityin some cases. Thus, a transistor using the oxide semiconductor as achannel region rarely has electrical characteristics in which athreshold voltage is negative (also referred to as normally-on). Ahighly purified intrinsic or substantially highly purified intrinsicoxide semiconductor has a low density of defect states and accordinglyhas a low density of trap states. Thus, the transistor using the oxidesemiconductor as the channel region has a small variation in electricalcharacteristics and high reliability. Charges trapped by the trap statesin the oxide semiconductor take a long time to be released and maybehave like fixed charges. Thus, the transistor which uses the oxidesemiconductor having a high density of trap states as a channel regionhas unstable electrical characteristics in some cases. As examples ofthe impurities, hydrogen, nitrogen, alkali metal, alkaline earth metal,and the like are given.

Hydrogen contained in the oxide semiconductor reacts with oxygen bondedto a metal atom to be water, and in addition, an oxygen vacancy isformed in a lattice from which oxygen is released (or a portion fromwhich oxygen is released). Due to entry of hydrogen into the oxygenvacancy, an electron serving as a carrier is generated. Further, in somecases, bonding of part of hydrogen to oxygen bonded to a metal elementcauses generation of an electron serving as a carrier. Thus, atransistor including an oxide semiconductor which contains hydrogen islikely to be normally on.

Accordingly, it is preferable that hydrogen be reduced as much aspossible in the oxide semiconductor film 18. Specifically, the hydrogenconcentration of the oxide semiconductor film 18, which is measured bysecondary ion mass spectrometry (SIMS), is lower than or equal to 2×10²⁰atoms/cm³, preferably lower than or equal to 5×10¹⁹ atoms/cm³, morepreferably lower than or equal to 1×10¹⁹ atoms/cm³, even more preferablylower than or equal to 5×10¹⁸ atoms/cm³, still more preferably lowerthan or equal to 1×10¹⁸ atoms/cm³, yet still more preferably lower thanor equal to 5×10¹⁷ atoms/cm³, even further more preferably lower than orequal to 1×10¹⁶ atoms/cm³.

As a method for reducing the hydrogen concentration of the oxidesemiconductor film 18, after the multilayer film 20 including the oxidesemiconductor film 18 and the oxide film 19 containing In or Ga areformed in FIG. 4B, heat treatment is performed; thus, the hydrogenconcentration of the oxide semiconductor film 18 can be reduced. Thetemperature of the heat treatment is typically higher than or equal to150° C. and lower than the strain point of the substrate, preferablyhigher than or equal to 200° C. and lower than or equal to 450° C., morepreferably higher than or equal to 300° C. and lower than or equal to450° C.

Further, the concentration of alkali metal or alkaline earth metal ofthe oxide semiconductor film 18, which is measured by secondary ion massspectrometry, is set to lower than or equal to 1×10¹⁸ atoms/cm³,preferably lower than or equal to 2×10¹⁶ atoms/cm³. Alkali metal andalkaline earth metal might generate carriers when bonded to an oxidesemiconductor, in which case the off-state current of the transistormight be increased. Therefore, it is preferable to reduce theconcentration of alkali metal or alkaline earth metal of the oxidesemiconductor film 18.

By providing a nitride insulating film in part of the gate insulatingfilm 17, the concentration of alkali metal or alkaline earth metal ofthe oxide semiconductor film 18 can be reduced.

Further, when containing nitrogen, the oxide semiconductor film 18easily has n-type conductivity by generation of electrons serving ascarriers and an increase of carrier density. Thus, a transistorincluding an oxide semiconductor which contains nitrogen is likely tohave normally-on characteristics. For this reason, nitrogen in the oxidesemiconductor film is preferably reduced as much as possible; theconcentration of nitrogen is preferably set to, for example, lower thanor equal to 5×10¹⁸ atoms/cm³.

In this manner, when the oxide semiconductor film 18 highly purified byreducing impurities (such as hydrogen, nitrogen, alkali metal, andalkaline earth metal) as much as possible is included, it is possible toinhibit making the transistor have normally-on characteristics, so thatthe off-state current of the transistor can be significantly reduced.Accordingly, a semiconductor device having favorable electricalcharacteristics can be manufactured. Further, a semiconductor devicewith improved reliability can be manufactured.

Various experiments can prove the low off-state current of a transistorincluding a highly purified oxide semiconductor film. For example, evenwhen an element has a channel width of 1×10⁶ μm and a channel length Lof 10 μm, off-state current can be less than or equal to the measurementlimit of a semiconductor parameter analyzer, i.e., less than or equal to1×10⁻¹³ A, at a voltage (drain voltage) between the source electrode andthe drain electrode of from 1 V to 10 V. In that case, it can be foundthat a value obtained by dividing the off-state current by the channelwidth of the transistor is less than or equal to 100 zA/μm. In addition,a capacitor and a transistor are connected to each other and theoff-state current is measured with a circuit in which charge flowinginto or from the capacitor is controlled by the transistor. In themeasurement, part of a highly purified oxide semiconductor film is usedfor a channel region of the transistor, and the off-state current of thetransistor is measured from a change in the amount of charge of thecapacitor per unit time. As a result, it is found that in the case wherethe voltage between the source electrode and the drain electrode of thetransistor is 3 V, lower off-state current of several tens ofyoctoamperes per micrometer (yA/μm) can be obtained. Thus, thetransistor including the highly purified oxide semiconductor film has asignificantly low off-state current.

Modification Example 3

As for the pair of electrodes 21 and 22 provided in the transistor 50described in this embodiment, it is preferable to use a conductivematerial which is easily bonded to oxygen, such as tungsten, titanium,aluminum, copper, molybdenum, chromium, or tantalum, or an alloythereof. Thus, oxygen contained in the multilayer film 20 and theconductive material contained in the pair of electrodes 21 and 22 arebonded to each other, so that an oxygen deficient region is formed inthe multilayer film 20. Further, in some cases, part of constituentelements of the conductive material that forms the pair of electrodes 21and 22 is mixed into the multilayer film 20. As a result of these, inthe multilayer film 20, a low-resistance region is formed in thevicinity of a region in contact with the pair of electrodes 21 and 22.FIGS. 5A to 5C are each an enlarged cross-sectional view of themultilayer film 20 of the transistor 50 shown in FIG. 1B.

There is a case where, as shown in FIG. 5A, large parts oflow-resistance regions 28 a and 29 a are formed in the oxide film 19containing In or Ga. There is another case where, as shown in FIG. 5B,low-resistance regions 28 b and 29 b are formed in the oxidesemiconductor film 18 and the oxide film 19 containing In or Ga. Thereis still another case where, as shown in FIG. 5C, low-resistance regions28 c and 29 c are formed in the oxide semiconductor film 18 and theoxide film 19 containing In or Ga so as to be in contact with the gateinsulating film 17. Since the low-resistance regions 28 a to 28 c and 29a to 29 c have high conductivity, contact resistance between themultilayer film 20 and the pair of electrodes 21 and 22 can be reduced,and thus, the on-state current of the transistor can be increased.

Further, the pair of electrodes 21 and 22 may each have a stacked-layerstructure of the conductive material which is easily bonded to oxygenand a conductive material which is not easily bonded to oxygen, such astitanium nitride, tantalum nitride, or ruthenium. With such astacked-layer structure, oxidization of the pair of electrodes 21 and 22can be prevented at the interface between the pair of electrodes 21 and22 and the oxide insulating film 23, so that the increase of theresistance of the pair of electrodes 21 and 22 can be inhibited.

Modification Example 4

In the method for manufacturing the transistor 50 described in thisembodiment, after the pair of electrodes 21 and 22 is formed, cleaningtreatment may be performed to remove an etching residue. By performingthe cleaning treatment, occurrence of leakage current flowing betweenthe pair of electrodes 21 and 22 can be inhibited. The cleaningtreatment can be performed using an alkaline solution such as atetramethylammonium hydroxide (TMAH) solution, an acidic solution suchas diluted hydrofluoric acid, an oxalic acid solution, or a phosphorusacid solution.

Modification Example 5

In the method for manufacturing the transistor 50 described in thisembodiment, after the pair of electrodes 21 and 22 is formed, themultilayer film 20 may be exposed to plasma generated in an oxygenatmosphere, so that oxygen may be supplied to the oxide semiconductorfilm 18 and the oxide film 19 containing In or Ga. Atmospheres ofoxygen, ozone, dinitrogen monoxide, nitrogen dioxide, and the like canbe given as examples of the oxygen atmosphere. Further, in the plasmatreatment, the multilayer film 20 is preferred to be exposed to plasmagenerated with no bias applied to the substrate 11 side. Consequently,the multilayer film 20 can be supplied with oxygen without beingdamaged, and the number of oxygen vacancies in the multilayer film 20can be reduced. Moreover, impurities remaining on the surface of themultilayer film 20 due to etching treatment, for example, a halogen suchas fluorine or chlorine can be removed.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 2

In this embodiment, a semiconductor device having a transistor in whichthe number of defects in the oxide semiconductor film can be furtherreduced as compared to Embodiment 1 is described with reference todrawings. The transistor described in this embodiment is different fromthat in Embodiment 1 in having an oxide film containing In or Ga betweenthe gate insulating film and the oxide semiconductor film.

FIGS. 6A to 6E are a top view and cross-sectional views of a transistor60 included in the semiconductor device. FIG. 6A is a top view of thetransistor 60, FIG. 6B is a cross-sectional view taken alongdashed-dotted line A-B of FIG. 6A, and FIG. 6C is a cross-sectional viewtaken along dashed-dotted line C-D of FIG. 6A. Note that in FIG. 6A, thesubstrate 11, the gate insulating film 17, the oxide insulating film 23,the oxide insulating film 24, the nitride insulating film 25, and thelike are omitted for simplicity.

The transistor 60 shown in FIGS. 6A to 6E includes the gate electrode 15provided over the substrate 11. Further, the gate insulating film 17 isformed over the substrate 11 and the gate electrode 15, and a multilayerfilm 34 overlapping with the gate electrode 15 with the gate insulatingfilm 17 provided therebetween, and the pair of electrodes 21 and 22 incontact with the multilayer film 34 are included. Furthermore, theprotective film 26 including the oxide insulating film 23, the oxideinsulating film 24, and the nitride insulating film 25 is formed overthe gate insulating film 17, the multilayer film 34, and the pair ofelectrodes 21 and 22.

In the transistor 60 described in this embodiment, the multilayer film34 includes an oxide film 31 containing In or Ga, an oxide semiconductorfilm 32, and an oxide film 33 containing In or Ga. Further, part of theoxide semiconductor film 32 serves as a channel region.

Further, the gate insulating film 17 and the oxide film 31 containing Inor Ga are in contact with each other. That is, the oxide film 31containing In or Ga is provided between the gate insulating film 17 andthe oxide semiconductor film 32.

Further, the oxide film 33 containing In and Ga and the oxide insulatingfilm 23 are in contact with each other. That is, the oxide film 33containing In or Ga is provided between the oxide semiconductor film 32and the oxide insulating film 23.

A material and a formation method which are similar to those of theoxide film 19 containing In or Ga in Embodiment 1 can be used for theoxide film 31 containing In or Ga and the oxide film 33 containing In orGa as appropriate.

Note that when the oxide film 31 containing In or Ga is In-M-Zn oxidefilm, the atomic ratio of In to M is preferably as follows: theproportion of In atoms be lower than 50 atomic % and the proportion of Matoms be higher than or equal to 50 atomic %, and it is furtherpreferably as follows: the proportion of In atoms be lower than 25atomic % and the proportion of M atoms be higher than or equal to 75atomic %.

Note that when the oxide film 33 containing In or Ga is In-M-Zn oxidefilm, the atomic ratio of In to M is preferably as follows: theproportion of In atoms be lower than 50 atomic % and the proportion of Matoms be higher than or equal to 50 atomic %, and it is furtherpreferably as follows: the proportion of In atoms be lower than 25atomic % and the proportion of M atoms be higher than or equal to 75atomic %.

A material and a formation method which are similar to those of theoxide semiconductor film 18 in Embodiment 1 can be used for the oxidesemiconductor film 32.

Here, as the oxide film 31 containing In or Ga, a 30-nm-thick In—Ga—Znoxide film (the atomic ratio of a sputtering target used for filmformation is In:Ga:Zn=1:6:4) is formed by a sputtering method. Further,as the oxide semiconductor film 32, a 10-nm-thick In—Ga—Zn oxide film(the atomic ratio of a sputtering target used for film formation isIn:Ga:Zn=1:1:1) is formed. Furthermore, as the oxide film 33 containingIn or Ga, a 10-nm-thick In—Ga—Zn oxide film (the atomic ratio of asputtering target used for film formation is In:Ga:Zn=1:3:2) is formed.

Here, the band structure along dashed-dotted line G-H in the vicinity ofthe multilayer film 34 of the transistor 60 in FIGS. 6A to 6E isdescribed with reference to FIG. 7A, and the flow of carrier in thetransistor 60 is described with reference to FIG. 7B.

In the band structure shown in FIG. 7A, for example, In—Ga—Zn oxide (theatomic ratio of a sputtering target used for film formation isIn:Ga:Zn=1:6:4) with an energy gap of 3.8 eV is used for the oxide film31 containing In or Ga. In—Ga—Zn oxide (the atomic ratio of a sputteringtarget used for film formation is In:Ga:Zn=1:1:1) with an energy gap of3.2 eV is used for the oxide semiconductor film 32. In—Ga—Zn oxide (theatomic ratio of a sputtering target used for film formation isIn:Ga:Zn=1:3:2) with an energy gap of 3.5 eV is used for the oxide film33 containing In or Ga.

The energy difference between the vacuum level and the valence band top(also referred to as ionization potential) of the oxide film 31containing In or Ga, the energy difference therebetween of the oxidesemiconductor film 32, and the energy difference therebetween of theoxide film 33 containing In or Ga are 7.8 eV, 7.9 eV, and 8.0 eV,respectively.

The energy difference between the vacuum level and the conduction bandbottom (also referred to as electron affinity) of the oxide film 31containing In or Ga, the energy difference therebetween of the oxidesemiconductor film 32, and the energy difference therebetween of theoxide film 33 containing In or Ga are 4.0 eV, 4.7 eV, and 4.5 eV,respectively.

Further, the conduction band bottom of the oxide film 31 containing Inor Ga is denoted by Ec_31, the conduction band bottom of the oxidesemiconductor film 32 is denoted by Ec_32, and the conduction bandbottom of the oxide film 33 containing In or Ga is denoted by Ec_33.Further, the conduction band bottom of the gate insulating film 17 isdenoted by Ec_17, and the conduction band bottom of the oxide insulatingfilm 23 is denoted by Ec_23.

As shown in FIG. 7A, in the multilayer film 34, the conduction bandbottom in the vicinity of the interface between the oxide film 31containing In or Ga and the oxide semiconductor film 32 and theconduction band bottom in the vicinity of the interface between theoxide semiconductor film 32 and the oxide film 33 containing In or Gavary continuously. That is, there is no barrier in the vicinity of theinterface between the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 and in the vicinity of the interface between theoxide semiconductor film 32 and the oxide film 33 containing In or Gaand the conduction band bottom smoothly varies. A structure having sucha conduction band bottom can also be referred to as a U-shaped well (Ushape well) structure. Such a shape is caused by mutual transfer ofoxygen between the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 and between the oxide semiconductor film 32 andthe oxide film 33 containing In or Ga. Further, in the multilayer film34, the energy of the conduction band bottom Ec_32 of the oxidesemiconductor film 32 is the lowest, and this region serves as a channelregion.

Now, a state where electrons serving as carrier flow in the transistor60 is described with reference to FIG. 7B. Note that in FIG. 7B, theflow of electrons flowing in the oxide semiconductor film 32 isrepresented by a dotted arrow.

Trap states 36 due to impurities and defects are formed in the vicinityof the interface between the gate insulating film 17 and the oxide film31 containing In or Ga. Further, trap states 37 are formed in thevicinity of the interface between the oxide film 33 containing In or Gaand the oxide insulating film 23 in a similar manner. In the transistor60 described in this embodiment, the oxide film 31 containing In or Gais provided between the gate insulating film 17 and the oxidesemiconductor film 32 as shown in FIG. 7B; thus, there is a distancebetween the oxide semiconductor film 32 and the trap states 36. Further,the oxide film 33 containing In or Ga is provided between the oxidesemiconductor film 32 and the oxide insulating film 23; thus, there is adistance between the oxide semiconductor film 32 and the trap states 37.

As a result, electrons flowing in the oxide semiconductor film 32 areless likely to be captured by the trap states 36 and 37, the on-statecurrent of the transistor can be increased, and field effect mobilitycan be increased. Further, when the electrons are captured by the trapstates 36 and 37, the electrons become negative fixed charges.Consequently, a threshold voltage of the transistor fluctuates. However,by the distance between the oxide semiconductor film 32 and the trapstates 36 and 37, capture of the electrons by the trap states 36 and 37can be reduced, and accordingly a fluctuation of the threshold voltagecan be reduced.

Note that when the energy difference ΔE2 of the conduction band bottomin the vicinity of the interface between the oxide film 31 containing Inor Ga and the oxide semiconductor film 32 and the energy difference ΔE3of the conduction band bottom in the oxide semiconductor film 32 and theoxide film 33 containing In or Ga are small, carrier flowing in theoxide semiconductor film 32 transcends the conduction band bottom of theoxide film 31 containing In or Ga and the conduction band bottom of theoxide film 33 containing In or Ga and is captured by the trap states 36and 37. Thus, the energy difference ΔE2 between the conduction bandbottoms of the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 and the energy difference ΔE3 between theconduction band bottoms of the oxide semiconductor film 32 and the oxidefilm 33 containing In or Ga are greater than or equal to 0.1 eV,preferably greater than or equal to 0.15 eV.

Note that when the energy difference ΔE3 in the vicinity of theinterface between the oxide semiconductor film 32 and the oxide film 33containing In or Ga is small as compared with the energy difference ΔE2in the vicinity of the interface between the oxide film 31 containing Inor Ga and the oxide semiconductor film 32, resistance between the oxidesemiconductor film 32 and the pair of electrodes 21 and 22 can bereduced and the number of electrons captured by the trap states 36 canbe reduced. Thus, the amount of on-state current of the transistor canbe further increased, and the field-effect mobility can be furtherincreased.

Although the energy difference ΔE3 is smaller than the energy differenceΔE2, the energy difference ΔE2 and the energy difference ΔE3 can be sameor the energy difference ΔE3 can be larger than the energy differenceΔE2 by selecting, as appropriate, constituent elements and compositionsof the oxide film 31 containing In or Ga, the oxide semiconductor film32, and the oxide film 33 containing In or Ga in accordance with theelectrical characteristics of the transistor.

Further, the oxide insulating film 24 (see FIGS. 6A to 6E) containingmore oxygen than that in the stoichiometric composition is provided onthe back channel side of the multilayer film 34 (a surface of themultilayer film 34, which is opposite to a surface facing the gateelectrode 15) with the oxide insulating film 23 through which oxygen ispermeated provided therebetween. Therefore, oxygen contained in theoxide insulating film 24 containing more oxygen than that in thestoichiometric composition is moved to the oxide semiconductor film 32included in the multilayer film 34, whereby oxygen vacancies in theoxide semiconductor film 32 can be reduced.

Although the multilayer film 34 is damaged by etching for forming thepair of electrodes 21 and 22 and oxygen vacancies are generated on theback channel side of the multilayer film 34, the oxygen vacancies can berepaired by oxygen contained in the oxide insulating film 24 containingmore oxygen than that in the stoichiometric composition. Accordingly,the reliability of the transistor 60 can be improved.

From the above, oxygen vacancies in the multilayer film 34 can bereduced by providing the multilayer film 34 including the oxide film 31containing In or Ga, the oxide semiconductor film 32, and the oxide film33 containing In or Ga, and the oxide insulating film 24 containing moreoxygen than that in the stoichiometric composition provided over themultilayer film 34 with the oxide insulating film 23 through whichoxygen is permeated provided therebetween. Further, the oxide film 31containing In or Ga is provided between the gate insulating film 17 andthe oxide semiconductor film 32, and the oxide film 33 containing In orGa is provided between the oxide semiconductor film 32 and the oxideinsulating film 23. Thus, it is possible to reduce the concentration ofsilicon or carbon in the vicinity of the interface between the oxidefilm 31 containing In or Ga and the oxide semiconductor film 32, theconcentration of silicon or carbon in the oxide semiconductor film 32,or the concentration of silicon or carbon in the vicinity of theinterface between the oxide film 33 containing In or Ga and the oxidesemiconductor film 32. Consequently, in the multilayer film 34, theabsorption coefficient derived from a constant photocurrent method islower than 1×10⁻³/cm, preferably lower than 1×10⁻⁴/cm, and thus densityof localized states is extremely low.

Since the transistor 60 having such a structure includes very fewdefects in the multilayer film 34 including the oxide semiconductor film32, the electrical characteristics of the transistor can be improved,and typically, the on-state current can be increased and thefield-effect mobility can be improved. Further, due to a BT stress testand a BT photostress test which are examples of a stress test, thethreshold voltage does not change or the amount of change in thenegative direction or the positive direction is less than or equal to1.0 V, preferably less than or equal to 0.5 V, and thus, reliability ishigh.

Modification Example 1

Instead of the multilayer film 34 which is described in this embodimentand shown in FIGS. 6A to 6C, a multilayer film 34 a including the oxidefilm 31 containing In or Ga, the oxide semiconductor film 32, the oxidefilm 33 containing In or Ga, and an oxide film 35 containing In or Gacan be used as shown in FIGS. 6D and 6E. Note that FIG. 6D correspondsto an enlarged view of the vicinity of the multilayer film 34 shown inFIG. 6B, and FIG. 6E corresponds to an enlarged view of the vicinity ofthe multilayer film 34 shown in FIG. 6C.

The oxide film 35 containing In or Ga is provided on the side surfacesof the oxide film 31 containing In or Ga, the oxide semiconductor film32, and the oxide film 33 containing In or Ga. That is, the oxidesemiconductor film 32 is surrounded by the oxide films each containingIn or Ga.

The oxide film 35 containing In or Ga is formed using metal oxide whichis similar to that of the oxide films 31 and 33 each containing In orGa. That is, the bandgap of the oxide film 35 containing In or Ga islarger than that of the oxide semiconductor film 32, and thus, it ispossible to inhibit capturing of an electron in a trap state in thevicinity of the interface between the multilayer film 34 a and the gateinsulating film 17 or a trap state in the vicinity of the interfacebetween the multilayer film 34 a and the oxide insulating film 23.Consequently, the reliability of the transistor is improved.

Note that the oxide film 35 containing In or Ga is formed in such amanner that a reaction product generated in a step of dry etching forforming the oxide film 31 containing In or Ga, the oxide semiconductorfilm 32, and the oxide film 33 containing In or Ga is attached to theside surfaces of the oxide film 31 containing In or Ga, the oxidesemiconductor film 32, and the oxide film 33 containing In or Ga. Thedry etching may be performed under conditions in which, for example, aboron trichloride gas and a chlorine gas are used as etching gases andinductively coupled plasma (ICP) power and substrate bias power areapplied.

Modification Example 2

In the transistor 60 described in this embodiment, the stacked-layerstructure of the multilayer film 34 and the pair of electrodes 21 and 22may be changed as appropriate. For example, a transistor 65 as shown inFIGS. 8A to 8C can be given as a modification example.

A top view of the transistor 65 is shown in FIG. 8A. A cross-sectionalview taken along dashed-dotted line A-B in FIG. 8A is shown in FIG. 8B,and a cross-sectional view taken along dashed-dotted line C-D is shownin FIG. 8C. Note that in FIG. 8A, the substrate 11, the gate insulatingfilm 17, the oxide film 31 containing In or Ga, the oxide semiconductorfilm 32, the protective film 26, and the like are omitted forsimplicity.

The transistor 65 is different from the transistor 60 in that part ofthe pair of electrodes 21 and 22 is surrounded by the oxidesemiconductor film 32 and the oxide film 33 containing In or Ga.Specifically, in the transistor 65, the oxide semiconductor film 32 isprovided over the oxide film 31 containing In or Ga, the pair ofelectrodes 21 and 22 is provided over the oxide semiconductor film 32,and the oxide film 33 containing In or Ga is provided in contact withthe oxide semiconductor film 32 and the pair of electrodes 21 and 22.Note that in the transistor 65, the stacked-layer structure of the othercomponents is the same as the stacked-layer structure in the transistor60.

The transistor 65 is a transistor in which the contact resistancebetween the multilayer film 34 and the pair of electrodes 21 and 22 islower than that of the transistor 60 and the on-state current isimproved as compared to the transistor 60 because the pair of electrodes21 and 22 is in contact with the oxide semiconductor film 32.

Further, since the pair of electrode 21 and 22 is in contact with theoxide semiconductor film 32 in the transistor 65, the oxide film 33containing In or Ga can be thickened without increase of the contactresistance between the multilayer film 34 and the pair of electrodes 21and 22. Thus, it is possible to inhibit formation of a trap state, whichoccurs due to plasma damage at the time of forming the protective film26, mixing of a constituent element of the protective film 26, or thelike, in the vicinity of the interface between the oxide semiconductorfilm 32 and the oxide film 33 containing In or Ga. That is, thetransistor 65 can achieve both improvement of on-state current andreduction of change in threshold voltage.

A method for manufacturing the transistor 65 is described with referenceto FIGS. 9A to 9D. First, in a manner similar to that of FIG. 4A, thegate electrode 15 and the gate insulating film 17 are formed over thesubstrate 11 (see FIG. 9A).

Next, an oxide film 44 containing In or Ga which is to be the oxide film31 containing In or Ga and an oxide semiconductor film 45 which is to bethe oxide semiconductor film 32 are successively formed, and then, thepair of electrodes 21 and 22 is formed (see FIG. 9B). A material and aformation method which are similar to those of the oxide film 19containing In or Ga described in Embodiment 1 can be used for the oxidefilm 44 containing In or Ga as appropriate. A material and a formationmethod which are similar to those of the oxide semiconductor film 18described in Embodiment 1 can be used for the oxide semiconductor film45 as appropriate. Further, the pair of electrodes 21 and 22 can beformed in a manner similar to that of FIG. 4C. Note that the pair ofelectrodes 21 and 22 is formed over the oxide semiconductor film 45.

Next, an oxide film containing In or Ga which is to be the oxide film 33containing In or Ga is formed to cover the oxide semiconductor film 45which is to be the oxide semiconductor film 32 and the pair ofelectrodes 21 and 22. A material and a formation method which aresimilar to those of the oxide film 19 containing In or Ga described inEmbodiment 1 can be used for the oxide film containing In or Ga asappropriate.

After that, the oxide film 44 containing In or Ga which is to be theoxide film 31 containing In or Ga, the oxide semiconductor film 45 whichis to be the oxide semiconductor film 32, and the oxide film containingIn or Ga which is to be the oxide film 33 containing In or Ga are eachpartly etched to form the multilayer film 34 including the oxide film 31containing In or Ga, the oxide semiconductor film 32, and the oxide film33 containing In or Ga (see FIG. 9C). Note that the etching can beimplemented with the use of a mask after the mask is formed by aphotolithography process over the oxide film containing In or Ga whichis to be the oxide film 33 containing In or Ga.

Next, the protective film 26 is formed to cover the gate insulating film17, the multilayer film 34, and the pair of electrodes 21 and 22. Theprotective film 26 can be formed in a manner similar to that inEmbodiment 1 (see FIG. 9D). Further, in the method for manufacturing thetransistor 65, heat treatment can be performed with reference toEmbodiment 1 as appropriate.

Further, by the etching for forming the pair of electrodes 21 and 22,defects such as oxygen vacancies are generated in the oxidesemiconductor film which is to be the oxide semiconductor film 32 andthe carrier density is increased in some cases; therefore, before theoxide film containing In or Ga which is to be the oxide film 33containing In or Ga is formed, the oxide semiconductor film ispreferably exposed to plasma generated in an oxygen atmosphere so thatoxygen is supplied to the oxide semiconductor film. Thus, in thetransistor 65, formation of a trap state in the vicinity of theinterface between the oxide semiconductor film 32 and the oxide film 33containing In or Ga can be inhibited, and change in threshold voltagecan be reduced. Further, in the transistor 65, leakage current thatflows in the vicinity of the side surface of the oxide semiconductorfilm 32 in the multilayer film 34 can be reduced, and increase ofoff-state current can be inhibited.

Although the multilayer film 34 is damaged by etching for forming thepair of electrodes 21 and 22 and oxygen vacancies are generated on theback channel side of the multilayer film 34, the oxygen vacancies can berepaired by oxygen contained in the oxide insulating film 24 containingmore oxygen than that in the stoichiometric composition. Accordingly,the reliability of the transistor 65 can be improved.

Modification Example 3

In the transistor 60 described in this embodiment, the stacked-layerstructure of the multilayer film 34 and the pair of electrodes 21 and 22may be changed as appropriate. For example, a transistor 66 as shown inFIGS. 10A to 10C can be given as a modification example.

A top view of the transistor 66 is shown in FIG. 10A. A cross-sectionalview taken along dashed-dotted line A-B in FIG. 10A is shown in FIG.10B, and a cross-sectional view taken along dashed-dotted line C-D isshown in FIG. 10C. Note that in FIG. 10A, the substrate 11, the gateinsulating film 17, the protective film 26, and the like are omitted forsimplicity.

The transistor 66 is different from the transistor 60 in that the oxidefilm 33 containing In or Ga is formed over the gate insulating film 17,the pair of electrodes 21 and 22, and the oxide semiconductor film 32.Specifically, in the transistor 66, the oxide semiconductor film 32 isprovided over the oxide film 31 containing In or Ga, the pair ofelectrodes 21 and 22 is provided to cover the oxide film 31 containingIn or Ga and the oxide semiconductor film 32, and the oxide film 33containing In or Ga is provided to cover the oxide film 31 containing Inor Ga, the oxide semiconductor film 32, and the pair of electrodes 21and 22. Note that in the transistor 66, the stacked-layer structure ofthe other components is the same as the stacked-layer structure of thetransistor 60.

The transistor 66 is a transistor in which the contact resistancebetween the multilayer film 34 and the pair of electrodes 21 and 22 islow and the on-state current is improved as compared to the transistor60 because the area of contact of the pair of electrodes 21 and 22 withthe oxide semiconductor film 32 is larger than that in the transistor60.

Further, since the area of contact of the pair of electrodes 21 and 22with the oxide semiconductor film 32 is large in the transistor 66, theoxide film 33 containing In or Ga can be thickened without increase ofthe contact resistance between the multilayer film 34 and the pair ofelectrodes 21 and 22. Thus, it is possible to inhibit formation of atrap state, which occurs due to plasma damage at the time of forming theprotective film 26, mixing of a constituent element of the protectivefilm 26, or the like, in the vicinity of the interface between the oxidesemiconductor film 32 and the oxide film 33 containing In or Ga. Thatis, the transistor 66 can achieve both improvement of on-state currentand reduction of change in threshold voltage.

A method for manufacturing the transistor 66 is described with referenceto FIGS. 11A to 11D. First, in a manner similar to that in FIG. 4A, thegate electrode and the gate insulating film 17 are formed over thesubstrate 11 (see FIG. 11A).

Next, the oxide film containing In or Ga which is to be the oxide film31 containing In or Ga and the oxide semiconductor film which is to bethe oxide semiconductor film 32 are successively formed, and a mask isprovided over the oxide semiconductor film by a photolithographyprocess, and etching is performed with the use of the mask to form theoxide film 31 containing In or Ga and the oxide semiconductor film 32.After that, the pair of electrodes 21 and 22 is formed to cover the edgeportions of the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 (see FIG. 11B). Note that a material and a filmformation method which are similar to those of the oxide film 19containing In or Ga in Embodiment 1 can be used for the oxide filmcontaining In or Ga as appropriate. A material and a film formationmethod which are similar to those of the oxide semiconductor film 18 inEmbodiment 1 can be used for the oxide semiconductor film asappropriate. Further, the pair of electrodes 21 and 22 can be formed ina manner similar to that shown in FIG. 4C.

Next, the oxide film 33 containing In or Ga is formed to cover the oxidesemiconductor film 32 and the pair of electrodes 21 and 22; thus, themultilayer film 34 is formed (see FIG. 11C). A material and a filmformation method which are similar to those of the oxide film 19containing In or Ga in Embodiment 1 can be used for the oxide filmcontaining In or Ga as appropriate. Note that the oxide film 33containing In or Ga may be processed by etching or the like using a maskformed by a photolithography process or the like as shown in FIG. 8B, ormay remain the state when the film was formed.

Next, the protective film 26 is formed over the gate insulating film 17and the oxide film 33 containing In or Ga. The protective film 26 can beformed in a manner similar to that in Embodiment 1 (see FIG. 11D).Further, in the method for manufacturing the transistor 66, heattreatment can be performed referring to Embodiment 1 as appropriate.

Further, by etching for forming the oxide film 31 containing In or Gaand the oxide semiconductor film 32, defects such as oxygen vacanciesare generated in the side surface of the oxide semiconductor film 32 andcarrier density is increased accordingly in some cases. Furthermore, byetching for forming the pair of electrodes 21 and 22, defects such asoxygen vacancies are generated in the surface of the oxide semiconductorfilm 32 and carrier density is increased accordingly in some cases.Therefore, after the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 are formed or/and after the pair of electrodes 21and 22 is formed, the oxide semiconductor film 32 is preferably exposedto plasma generated in an oxygen atmosphere so that oxygen is suppliedto the oxide semiconductor film 32.

Although the multilayer film 34 is damaged by etching for forming thepair of electrodes 21 and 22 and oxygen vacancies are generated on theback channel side of the multilayer film 34, the oxygen vacancies can berepaired by oxygen contained in the oxide insulating film 24 containingmore oxygen than that in the stoichiometric composition. Accordingly,the reliability of the transistor 66 can be improved.

Thus, in the transistor 66, formation of a trap state in the sidesurface of the oxide semiconductor film 32 and in the vicinity of theinterface between the oxide semiconductor film 32 and the oxide film 33containing In or Ga can be inhibited, and change in threshold voltagecan be reduced.

Further, in the transistor 66, the oxide film 33 containing In or Ga isprovided to cover the side surfaces (the side surfaces in the channellength direction) of the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 (see FIG. 10C). Thus, leakage current that flowsin the side surface of the oxide semiconductor film 32 can be reduced,and increase of off-state current can be inhibited.

Further, when the oxide film 31 containing In or Ga and the oxidesemiconductor film 32 are formed (see FIG. 10B), in an etching step inwhich the oxide film 31 containing In or Ga is formed after the oxidesemiconductor film 32 is formed, there may be a case where a reactionproduct is attached on the side surfaces of the oxide film 31 containingIn or Ga and the oxide semiconductor film 32 to form an oxide filmcontaining In or Ga (corresponding to the oxide film 35 containing In orGa shown in FIG. 6D). In this case, the oxide film 33 containing In orGa is formed to cover the oxide film containing In or Ga that covers theside surface of the oxide semiconductor film 32.

Modification Example 4

In the transistor 60 described in this embodiment, the stacked-layerstructure of the multilayer film 34 and the pair of electrodes 21 and 22may be changed as appropriate. For example, a transistor 67 as shown inFIGS. 12A to 12C can be given as a modification example.

A top view of the transistor 67 is shown in FIG. 12A. A cross-sectionalview taken along dashed-dotted line A-B in FIG. 12A is shown in FIG.12B, and a cross-sectional view taken along dashed-dotted line C-D isshown in FIG. 12C. Note that in FIG. 12A, the substrate 11, the gateinsulating film 17, the protective film 26, and the like are omitted forsimplicity.

In the transistor 67, the oxide film 33 containing In or Ga is providedto cover the pair of electrodes 21 and 22 and the edge portions of theoxide film 33 containing In or Ga are located over the pair ofelectrodes 21 and 22 in the transistor 66 shown in FIG. 10B. Note thatin the transistor 67, the stacked-layer structure of the othercomponents is the same as the stacked-layer structure of the transistor66.

In the transistor 67, as shown in FIG. 12C, the oxide film 33 containingIn or Ga is provided to cover the side surfaces of the oxide film 31containing In or Ga and the oxide semiconductor film 32 on the sidesurfaces intersecting with the channel width direction. Thus, leakagecurrent that flows in the side surface of the oxide semiconductor film32 can be reduced, and increase of off-state current can be inhibited.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 3

In this embodiment, a transistor having a different structure from thetransistors in Embodiment 1 and Embodiment 2 is described with referenceto FIG. 13. A transistor 70 described in this embodiment includes aplurality of gate electrodes facing each other with an oxidesemiconductor film provided therebetween.

The transistor 70 shown in FIG. 13 includes the gate electrode 15provided over the substrate 11. Further, the gate insulating film 17 isformed over the substrate 11 and the gate electrode 15, and themultilayer film 20 overlapping with the gate electrode 15 with the gateinsulating film 17 provided therebetween, and the pair of electrodes 21and 22 in contact with the multilayer film 20 are included. Note thatthe multilayer film 20 includes the oxide semiconductor film 18 and theoxide film 19 containing In or Ga. Furthermore, the protective film 26including the oxide insulating film 23, the oxide insulating film 24,and the nitride insulating film 25 is formed over the gate insulatingfilm 17, the multilayer film 20, and the pair of electrodes 21 and 22.Still furthermore, a gate electrode 61 overlapping with the multilayerfilm 20 with the protective film 26 provided therebetween is included.

The gate electrode 61 can be formed in a manner similar to that of thegate electrode 15 in Embodiment 1.

The transistor 70 described this embodiment has the gate electrode 15and the gate electrode 61 facing each other with the multilayer film 20provided therebetween. By applying different potentials to the gateelectrode 15 and the gate electrode 61, the threshold voltage of thetransistor 70 can be controlled.

Further, when the multilayer film 20 having the oxide semiconductor film18 in which the number of oxygen vacancies is reduced is included, theelectrical characteristics of the transistor can be improved. Further,the transistor in which the amount of change in threshold voltage issmall and which is highly reliable is obtained.

Although the oxide semiconductor film which is described in the aboveembodiments can be formed by a sputtering method, such film may beformed by another method, e.g., a thermal CVD method. A metal organicchemical vapor deposition (MOCVD) method or an atomic layer deposition(ALD) method may be employed as an example of a thermal CVD method.

A thermal CVD method has an advantage that no defect due to plasmadamage is generated since it does not utilize plasma for forming a film.

Deposition by a thermal CVD method may be performed in such a mannerthat the pressure in a chamber is set to an atmospheric pressure or areduced pressure, and a source gas and an oxidizer are supplied to thechamber at a time and react with each other in the vicinity of thesubstrate or over the substrate.

Deposition by an ALD method may be performed in such a manner that thepressure in a chamber is set to an atmospheric pressure or a reducedpressure, source gases for reaction are sequentially introduced into thechamber, and then the sequence of the gas introduction is repeated. Forexample, two or more kinds of source gases are sequentially supplied tothe chamber by switching respective switching valves (also referred toas high-speed valves). For example, a first source gas is introduced, aninert gas (e.g., argon or nitrogen) or the like is introduced at thesame time as or after the introduction of the first gas so that thesource gases are not mixed, and then a second source gas is introduced.Note that in the case where the first source gas and the inert gas areintroduced at a time, the inert gas serves as a carrier gas, and theinert gas may also be introduced at the same time as the introduction ofthe second source gas. Alternatively, the first source gas may beexhausted by vacuum evacuation instead of the introduction of the inertgas, and then the second source gas may be introduced. The first sourcegas is adsorbed on the surface of the substrate to form a firstsingle-atomic layer; then the second source gas is introduced to reactwith the first single-atomic layer; as a result, a second single-atomiclayer is stacked over the first single-atomic layer, so that a thin filmis formed. The sequence of the gas introduction is repeated plural timesuntil a desired thickness is obtained, whereby a thin film withexcellent step coverage can be formed. The thickness of the thin filmcan be adjusted by the number of repetitions times of the sequence ofthe gas introduction; therefore, an ALD method makes it possible toaccurately adjust a thickness and thus is suitable for manufacturing aminute FET.

The oxide semiconductor film which is described in the above embodimentscan be formed by a thermal CVD method such as a MOCVD method or an ALDmethod. For example, in the case where an InGaZnO_(X) (X>0) film isformed, trimethylindium, trimethylgallium, and diethylzinc are used.Note that the chemical formula of trimethylindium is (CH₃)₃In. Thechemical formula of trimethylgallium is (CH₃)₃Ga. The chemical formulaof diethylzinc is (CH₃)₂Zn. Without limitation to the above combination,triethylgallium (chemical formula: (C₂H₅)₃Ga) can be used instead oftrimethylgallium and dimethylzinc (chemical formula: (C₂H₅)₂Zn) can beused instead of diethylzinc.

For example, in the case where an oxide semiconductor film, e.g., anInGaZnO_(X) (X>0) film is formed using a deposition apparatus employingALD, an In(CH₃)₃ gas and an O₃ gas are sequentially introduced pluraltimes to form an InO₂ layer, a Ga(CH₃)₃ gas and an O₃ gas are introducedat a time to form a GaO layer, and then a Zn(CH₃)₂ gas and an O₃ gas areintroduced at a time to form a ZnO layer. Note that the order of theselayers is not limited to this example. A mixed compound layer such as anInGaO₂ layer, an InZnO₂ layer, a GaInO layer, a ZnInO layer or a GaZnOlayer may be formed by mixing of these gases. Note that although an H₂Ogas which is obtained by bubbling with an inert gas such as Ar may beused instead of an O₃ gas, it is preferable to use an O₃ gas, which doesnot contain H. Further, instead of an In(CH₃)₃ gas, an In(C₂H₅)₃ gas maybe used. Instead of a Ga(CH₃)₃ gas, a Ga(C₂H₅)₃ gas may be used. Insteadof an In(CH₃)₃ gas, an In(C₂H₅)₃ may be used. Furthermore, a Zn(CH₃)₂gas may be used.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 4

In this embodiment, one embodiment which can be applied to an oxidesemiconductor film in the transistor included in the semiconductordevice described in the above embodiment is described.

The oxide semiconductor film can be formed using any of an amorphousoxide semiconductor, a single crystal oxide semiconductor, and apolycrystalline oxide semiconductor. Alternatively, the oxidesemiconductor film may be formed using an oxide semiconductor includinga crystalline portion (CAAC-OS).

The CAAC-OS film is one of oxide semiconductor films including aplurality of crystal parts, and most of the crystal parts each fitinside a cube whose one side is less than 100 nm. Thus, there is a casewhere a crystal part included in the CAAC-OS film fits a cube whose oneside is less than 10 nm, less than 5 nm, or less than 3 nm. The densityof defect states of the CAAC-OS film is lower than that of themicrocrystalline oxide semiconductor film. The CAAC-OS film is describedin detail below.

In a transmission electron microscope (TEM) image of the CAAC-OS film, aboundary between crystal parts, that is, a grain boundary is not clearlyobserved. Thus, in the CAAC-OS film, a reduction in electron mobilitydue to the grain boundary is less likely to occur.

According to the TEM image of the CAAC-OS film observed in a directionsubstantially parallel to a sample surface (cross-sectional TEM image),metal atoms are arranged in a layered manner in the crystal parts. Eachmetal atom layer has a morphology reflected by a surface over which theCAAC-OS film is formed (hereinafter, a surface over which the CAAC-OSfilm is formed is referred to as a formation surface) or a top surfaceof the CAAC-OS film, and is arranged in parallel to the formationsurface or the top surface of the CAAC-OS film.

On the other hand, according to the TEM image of the CAAC-OS filmobserved in a direction substantially perpendicular to the samplesurface (plan TEM image), metal atoms are arranged in a triangular orhexagonal configuration in the crystal parts. However, there is noregularity of arrangement of metal atoms between different crystalparts.

From the results of the cross-sectional TEM image and the plan TEMimage, alignment is found in the crystal parts in the CAAC-OS film.

A CAAC-OS film is subjected to structural analysis with an X-raydiffraction (XRD) apparatus. For example, when the CAAC-OS filmincluding an InGaZnO₄ crystal is analyzed by an out-of-plane method, apeak appears frequently when the diffraction angle (2θ) is around 31°.This peak is derived from the (009) plane of the InGaZnO₄ crystal, whichindicates that crystals in the CAAC-OS film have c-axis alignment, andthat the c-axes are aligned in a direction substantially perpendicularto the formation surface or the top surface of the CAAC-OS film.

On the other hand, when the CAAC-OS film is analyzed by an in-planemethod in which an X-ray enters a sample in a direction substantiallyperpendicular to the c-axis, a peak appears frequently when 2θ is around56°. This peak is derived from the (110) plane of the InGaZnO₄ crystal.Here, analysis (φ scan) is performed under conditions where the sampleis rotated around a normal vector of a sample surface as an axis (φaxis) with 2θ fixed at around 56°. In the case where the sample is asingle-crystal oxide semiconductor film of InGaZnO₄, six peaks appear.The six peaks are derived from crystal planes equivalent to the (110)plane. On the other hand, in the case of a CAAC-OS film, a peak is notclearly observed even when φ scan is performed with 2θ fixed at around56°.

According to the above results, in the CAAC-OS film having c-axisalignment, while the directions of a-axes and b-axes are differentbetween crystal parts, the c-axes are aligned in a direction parallel toa normal vector of a formation surface or a normal vector of a topsurface. Thus, each metal atom layer arranged in a layered mannerobserved in the cross-sectional TEM image corresponds to a planeparallel to the a-b plane of the crystal.

Note that the crystal part is formed concurrently with deposition of theCAAC-OS film or is formed through crystallization treatment such as heattreatment. As described above, the c-axis of the crystal is aligned in adirection parallel to a normal vector of a formation surface or a normalvector of a top surface. Thus, for example, in the case where a shape ofthe CAAC-OS film is changed by etching or the like, the c-axis might notbe necessarily parallel to a normal vector of a formation surface or anormal vector of a top surface of the CAAC-OS film.

Further, the degree of crystallinity in the CAAC-OS film is notnecessarily uniform. For example, in the case where crystal growthleading to the CAAC-OS film occurs from the vicinity of the top surfaceof the film, the degree of the crystallinity in the vicinity of the topsurface is higher than that in the vicinity of the formation surface insome cases. Further, when an impurity is added to the CAAC-OS film, thecrystallinity in a region to which the impurity is added is changed, andthe degree of crystallinity in the CAAC-OS film varies depending onregions.

Note that when the CAAC-OS film with an InGaZnO₄ crystal is analyzed byan out-of-plane method, a peak of 2θ may also be observed at around 36°,in addition to the peak of 2θ at around 31°. The peak of 2θ at around36° indicates that a crystal having no c-axis alignment is included inpart of the CAAC-OS film. It is preferable that in the CAAC-OS film, apeak of 2θ appear at around 31° and a peak of 2θ do not appear at around36°.

There are three methods for forming a CAAC-OS film.

The first method is to form an oxide semiconductor film at a temperaturehigher than or equal to 150° C. and lower than or equal to 500° C.,preferably higher than or equal to 150° C. and lower than or equal to450° C., more preferably higher than or equal to 200° C. and lower thanor equal to 350° C., whereby crystal parts in which the c-axes arealigned in the direction parallel to a normal vector of a surface onwhich the oxide semiconductor film is formed or a normal vector of asurface of the oxide semiconductor film are formed in the oxidesemiconductor film.

The second method is to form an oxide semiconductor film with a smallthickness and then heat it at a temperature higher than or equal to 200°C. and lower than or equal to 700° C., whereby crystal parts in whichthe c-axes are aligned in the direction parallel to a normal vector of asurface on which the oxide semiconductor film is formed or a normalvector of a surface of the oxide semiconductor film are formed in theoxide semiconductor film.

The third method is to form a first oxide semiconductor film with asmall thickness, then heat it at a temperature higher than or equal to200° C. and lower than or equal to 700° C., and form a second oxidesemiconductor film, whereby crystal parts in which the c-axes arealigned in the direction parallel to a normal vector of a surface onwhich the oxide semiconductor film is formed or a normal vector of asurface of the oxide semiconductor film are formed in the oxidesemiconductor film.

In a transistor using the CAAC-OS for an oxide semiconductor film,variations in electric characteristics of the transistor due toirradiation with visible light or ultraviolet light is small. Thus, thetransistor using the CAAC-OS for the oxide semiconductor film has highreliability.

For example, the CAAC-OS is formed by a sputtering method with apolycrystalline oxide semiconductor sputtering target. When ions collidewith the sputtering target, a crystal region included in the sputteringtarget may be separated from the target along an a-b plane; in otherwords, a sputtered particle having a plane parallel to an a-b plane(flat-plate-like sputtered particle or pellet-like sputtered particle)may flake off from the sputtering target. In that case, theflat-plate-like sputtered particle or the pellet-like sputtered particlereaches a surface on which the CAAC-OS is formed while maintaining itscrystal state, whereby the CAAC-OS can be deposited.

For the deposition of the CAAC-OS, the following conditions arepreferably employed.

By reducing the number of impurities entering the CAAC-OS during thedeposition, the crystal state can be inhibited from being broken by theimpurities. For example, the concentration of impurities (e.g.,hydrogen, water, carbon dioxide, or nitrogen) which exist in thedeposition chamber may be reduced. Furthermore, the concentration ofimpurities in a deposition gas may be reduced. Specifically, adeposition gas whose dew point is lower than or equal to −80° C.,preferably lower than or equal to −100° C. is used.

By increasing the heating temperature of the surface on which theCAAC-OS is formed (e.g., the substrate heating temperature) during thedeposition, migration of a sputtered particle is likely to occur afterthe sputtered particle reaches the surface on which the CAAC-OS isformed. Specifically, the temperature of the surface on which theCAAC-OS is formed during the deposition is higher than or equal to 100°C. and lower than or equal to 740° C., preferably higher than or equalto 200° C. and lower than or equal to 500° C. By increasing thetemperature of the surface on which the CAAC-OS is formed during thedeposition, when the flat-plate-like or pellet-like sputtered particlereaches the surface on which the CAAC-OS is formed, migration occurs onthe surface on which the CAAC-OS is formed, so that a flat plane of thesputtered particle is attached to the surface on which the CAAC-OS isformed.

Furthermore, it is preferable that the proportion of oxygen in thedeposition gas be increased and the power be optimized in order toreduce plasma damage at the deposition. The proportion of oxygen in thedeposition gas is higher than or equal to 30 vol %, preferably 100 vol%.

As an example of the sputtering target, an In—Ga—Zn-based compoundtarget is described below.

The polycrystalline In—Ga—Zn-based compound target is made by mixingInO_(X) powder, GaO_(Y) powder, and ZnO_(Z) powder in a predeterminedmolar ratio, applying pressure, and performing heat treatment at atemperature higher than or equal to 1000° C. and lower than or equal to1500° C. This pressure treatment may be performed while cooling isperformed or may be performed while heating is performed. Note that X,Y, and Z are each a given positive number. Here, the predetermined molarratio of InO_(X) powder to GaO_(Y) powder and ZnO_(Z) powder is, forexample, 2:2:1, 8:4:3, 3:1:1, 1:1:1, 4:2:3, 3:1:2, 1:3:2, 1:6:4, or1:9:6. The kinds of powder and the molar ratio for mixing powder may bedetermined as appropriate depending on the desired sputtering target.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 5

A semiconductor device (also referred to as a display device) having adisplay function can be manufactured using the transistor examples ofwhich are shown in the above embodiments. Moreover, some or all of thedriver circuits which include the transistor can be formed over asubstrate where the pixel portion is formed, whereby a system-on-panelcan be obtained. In this embodiment, an example of a display deviceusing the transistor examples of which are shown in the aboveembodiments is described with reference to FIGS. 14A to 14C and FIGS.15A and 15B. FIGS. 15A and 15B are cross-sectional views illustratingcross-sectional structures taken along dashed-dotted line M-N in FIG.14B.

In FIG. 14A, a sealant 905 is provided so as to surround a pixel portion902 provided over a first substrate 901, and the pixel portion 902 issealed with a second substrate 906. In FIG. 14A, a signal line drivercircuit 903 and a scan line driver circuit 904 each are formed using asingle crystal semiconductor or a polycrystalline semiconductor over asubstrate prepared separately, and mounted in a region different fromthe region surrounded by the sealant 905 over the first substrate 901.Further, various signals and potentials are supplied to the signal linedriver circuit 903, the scan line driver circuit 904, and the pixelportion 902 from a flexible printed circuit (FPC) 918.

In FIGS. 14B and 14C, the sealant 905 is provided so as to surround thepixel portion 902 and the scan line driver circuit 904 which areprovided over the first substrate 901. The second substrate 906 isprovided over the pixel portion 902 and the scan line driver circuit904. Thus, the pixel portion 902 and the scan line driver circuit 904are sealed together with a display element by the first substrate 901,the sealant 905, and the second substrate 906. In FIGS. 14B and 14C, asignal line driver circuit 903 which is formed using a single crystalsemiconductor or a polycrystalline semiconductor over a substrateseparately prepared is mounted in a region different from the regionsurrounded by the sealant 905 over the first substrate 901. In FIGS. 14Band 14C, various signals and potentials are supplied to the signal linedriver circuit 903, the scan line driver circuit 904, and the pixelportion 902 from an FPC 918.

Although FIGS. 14B and 14C each show an example in which the signal linedriver circuit 903 is formed separately and mounted on the firstsubstrate 901, one embodiment of the present invention is not limited tothis structure. The scan line driver circuit may be separately formedand then mounted, or only part of the signal line driver circuit or partof the scan line driver circuit may be separately formed and thenmounted.

Note that a connection method of a separately formed driver circuit isnot particularly limited, and a chip on glass (COG) method, a wirebonding method, a tape automated bonding (TAB) method, or the like canbe used. FIG. 14A shows an example in which the signal line drivercircuit 903 and the scan line driver circuit 904 are mounted by a COGmethod. FIG. 14B shows an example in which the signal line drivercircuit 903 is mounted by a COG method. FIG. 14C shows an example inwhich the signal line driver circuit 903 is mounted by a TAB method.

The display device includes in its category a panel in which a displayelement is sealed and a module in which an IC including a controller orthe like is mounted on the panel.

A display device in this specification refers to an image display deviceor a light source (including a lighting device). Further, the displaydevice also includes the following modules in its category: a module towhich a connector such as an FPC or a TCP is attached; a module having aTCP at the tip of which a printed wiring board is provided; and a modulein which an integrated circuit (IC) is directly mounted on a displayelement by a COG method.

The pixel portion and the scan line driver circuit provided over thefirst substrate include a plurality of transistors and any of thetransistors which are described in the above embodiments can be used.

As the display element provided in the display device, a liquid crystalelement (also referred to as a liquid crystal display element) or alight-emitting element (also referred to as a light-emitting displayelement) can be used. A light emitting element includes, in its scope,an element whose luminance is controlled by current or voltage, andspecifically includes an inorganic electroluminescent (EL) element, anorganic EL element, and the like. Further, a display medium whosecontrast is changed by an electric effect, such as electronic ink, canbe used. FIG. 15A illustrates an example of a liquid crystal displaydevice using a liquid crystal element as the display element and FIG.15B illustrates an example of a light-emitting display device using alight-emitting element as the display element.

As illustrated in FIGS. 15A and 15B, the display device includes aconnection terminal electrode 915 and a terminal electrode 916. Theconnection terminal electrode 915 and the terminal electrode 916 areelectrically connected to a terminal included in the FPC 918 through ananisotropic conductive agent 919.

The connection terminal electrode 915 is formed using the sameconductive film as a first electrode 930, and the terminal electrode 916is formed using the same conductive film as a pair of electrodes in eachof a transistor 910 and a transistor 911.

Each of the pixel portion 902 and the scan line driver circuit 904 whichare provided over the first substrate 901 includes a plurality oftransistors. FIGS. 15A and 15B illustrate the transistor 910 included inthe pixel portion 902 and the transistor 911 included in the scan linedriver circuit 904. In FIG. 15A, an insulating film 924 is provided overeach of the transistor 910 and the transistor 911, and in FIG. 15B, aplanarization film 921 is further provided over the insulating film 924.Note that as a multilayer film 926 including an oxide semiconductor filmin each of the transistors 910 and 911, the multilayer film 20 includingan oxide semiconductor film described in Embodiment 1 or the multilayerfilm 34 including an oxide semiconductor film described in Embodiment 2can be used as appropriate. As the insulating film 924, the protectivefilm 26 described in Embodiment 1 can be used as appropriate. Theinsulating film 923 is an insulating film serving as a base film.

In this embodiment, any of the transistors described in the aboveembodiments can be used as the transistor 910 and the transistor 911 asappropriate. Any of the transistors described in Embodiment 1 toEmbodiment 3 is used as the transistors 910 and 911, whereby a displaydevice with high image quality can be fabricated.

Moreover, FIG. 15B shows an example in which a conductive film 917 isprovided over the planarization film 921 so as to overlap with a channelregion of the multilayer film 926 of the transistor 911 for the drivercircuit. In this embodiment, the conductive film 917 is formed using theconductive film which is used as the first electrode 930. By providingthe conductive film 917 so as to overlap with the channel region of themultilayer film 926, the amount of change in the threshold voltage ofthe transistor 911 between before and after a BT stress test can befurther reduced. The conductive film 917 may have the same potential asor a potential different from that of the gate electrode of thetransistor 911, and the conductive film 917 can serve as a second gateelectrode. The potential of the conductive film 917 may be GND, 0 V, ina floating state, or the same potential or substantially the samepotential as the minimum potential (Vss; for example, the potential ofthe source electrode in the case where the potential of the sourceelectrode is a reference potential) of the driver circuit.

In addition, the conductive film 917 has a function of blocking anexternal electric field. In other words, the conductive film 917 has afunction of preventing an external electric field (particularly, afunction of preventing static electricity) from affecting the inside (acircuit portion including the transistor). Such a blocking function ofthe conductive film 917 can prevent a change in electricalcharacteristics of the transistor due to the influence of an externalelectric field such as static electricity. The conductive film 917 canbe used for any of the transistors described in the above embodiments.

In the display panel, the transistor 910 included in the pixel portion902 is electrically connected to a display element. There is noparticular limitation on the kind of the display element as long asdisplay can be performed, and various kinds of display elements can beused.

In FIG. 15A, a liquid crystal element 913 which is a display elementincludes the first electrode 930, a second electrode 931, and a liquidcrystal layer 908. Note that an insulating film 932 and an insulatingfilm 933 which serve as alignment films are provided so that the liquidcrystal layer 908 is provided therebetween. The second electrode 931 isprovided on the second substrate 906 side. The second electrode 931overlaps with the first electrode 930 with the liquid crystal layer 908provided therebetween.

A spacer 935 is a columnar spacer obtained by selective etching of aninsulating film and is provided in order to control the distance betweenthe first electrode 930 and the second electrode 931 (a cell gap).Alternatively, a spherical spacer may be used.

In the case where a liquid crystal element is used as the displayelement, a thermotropic liquid crystal, a low-molecular liquid crystal,a high-molecular liquid crystal, a polymer-dispersed liquid crystal, aferroelectric liquid crystal, an anti-ferroelectric liquid crystal, orthe like can be used. Such a liquid crystal material exhibits acholesteric phase, a smectic phase, a cubic phase, a chiral nematicphase, an isotropic phase, or the like depending on a condition.

Alternatively, a liquid crystal exhibiting a blue phase for which analignment film is unnecessary may be used. A blue phase is one of liquidcrystal phases, which is generated just before a cholesteric phasechanges into an isotropic phase while temperature of cholesteric liquidcrystal is raised. Since the blue phase appears only in a narrowtemperature range, a liquid crystal composition in which a chiralmaterial is mixed is used for the liquid crystal layer in order toimprove the temperature range. The liquid crystal composition whichincludes a liquid crystal showing a blue phase and a chiral material hasa short response time of 1 msec or less, and has optical isotropy, whichmakes the alignment process unneeded and viewing angle dependence small.In addition, since an alignment film does not need to be provided andrubbing treatment is unnecessary, electrostatic discharge damage causedby the rubbing treatment can be prevented and defects and damage of theliquid crystal display device in the manufacturing process can bereduced. Thus, the productivity of the liquid crystal display device canbe increased.

The first substrate 901 and the second substrate 906 are fixed in placeby the sealant 925. As the sealant 925, an organic resin such as athermosetting resin or a photocurable resin can be used.

Further, the transistor including an oxide semiconductor film used inthe above embodiments has excellent switching characteristics.Furthermore, relatively high field-effect mobility is obtained, whichenables high-speed operation. Consequently, when the above transistor isused in a pixel portion of a semiconductor device having a displayfunction, high-quality images can be obtained. Since a driver circuitportion and the pixel portion can be formed over one substrate with theuse of the above transistor, the number of components of thesemiconductor device can be reduced.

The size of storage capacitor formed in the liquid crystal displaydevice is set considering the leakage current of the transistor providedin the pixel portion or the like so that charge can be held for apredetermined period. By using the transistor including thehighly-purified oxide semiconductor film, it is enough to provide astorage capacitor having a capacitance that is ⅓ or less, preferably ⅕or less of a liquid crystal capacitance of each pixel; therefore, theaperture ratio of a pixel can be increased.

In the display device, a black matrix (a light-blocking film), anoptical member (an optical substrate) such as a polarizing member, aretardation member, or an anti-reflection member, and the like areprovided as appropriate. For example, circular polarization may beobtained by using a polarizing substrate and a retardation substrate. Inaddition, a backlight, a side light, or the like may be used as a lightsource.

As a display method in the pixel portion, a progressive method, aninterlace method, or the like can be used. Further, color elementscontrolled in a pixel at the time of color display are not limited tothree colors: R, G, and B (R, G, and B correspond to red, green, andblue, respectively). For example, R, G, B, and W (W corresponds towhite), or R, G, B, and one or more of yellow, cyan, magenta, and thelike can be used. Further, the sizes of display regions may be differentbetween respective dots of color elements. One embodiment of the presentinvention is not limited to the application to a display device forcolor display but can also be applied to a display device for monochromedisplay.

In FIG. 15B, a light-emitting element 963 which is a display element iselectrically connected to the transistor 910 provided in the pixelportion 902. Note that although the structure of the light-emittingelement 963 is a stacked-layer structure of the first electrode 930, alight-emitting layer 961, and the second electrode 931, the structure isnot limited thereto. The structure of the light-emitting element 963 canbe changed as appropriate depending on the direction in which light isextracted from the light-emitting element 963, or the like.

A partition wall 960 can be formed using an organic insulating materialor an inorganic insulating material. It is particularly preferred thatthe partition wall 960 be formed using a photosensitive resin materialto have an opening over the first electrode 930 so that a sidewall ofthe opening has an inclined surface with a continuous curvature.

The light-emitting layer 961 may be formed to have a single-layerstructure or a stacked-layer structure including a plurality of layers.

A protective layer may be formed over the second electrode 931 and thepartition wall 960 in order to prevent oxygen, hydrogen, moisture,carbon dioxide, or the like from entering the light-emitting element963. As the protective layer, a silicon nitride film, a silicon nitrideoxide film, an aluminum oxide film, an aluminum nitride film, analuminum oxynitride film, an aluminum nitride oxide film, a DLC film, orthe like can be formed. In addition, in a space which is sealed with thefirst substrate 901, the second substrate 906, and a sealant 936, afiller 964 is provided and sealed. It is preferred that, in this manner,the light-emitting element be packaged (sealed) with a protective film(such as a laminate film or an ultraviolet curable resin film) or acover material with high air-tightness and little degasification so thatthe panel is not exposed to the outside air.

As the sealant 936, an organic resin such as a thermosetting resin or aphotocurable resin, fritted glass including low-melting glass, or thelike can be used. The fritted glass is preferred because of its highbarrier property against impurities such as water and oxygen. Further,in the case where the fritted glass is used as the sealant 936, asillustrated in FIG. 15B, the fritted glass is provided over theinsulating film 924, whereby adhesion of the insulating film 924 to thefritted glass becomes high, which is preferable.

As the filler 964, as well as an inert gas such as nitrogen or argon, anultraviolet curable resin or a thermosetting resin can be used:polyvinyl chloride (PVC), an acrylic resin, polyimide, an epoxy resin, asilicone resin, polyvinyl butyral (PVB), ethylene vinyl acetate (EVA),or the like can be used. For example, nitrogen is used for the filler.

If necessary, an optical film such as a polarizing plate, a circularlypolarizing plate (including an elliptically polarizing plate), aretardation plate (a quarter-wave plate or a half-wave plate), or acolor filter may be provided as appropriate for a light-emitting surfaceof the light-emitting element. Further, a polarizing plate or acircularly polarizing plate may be provided with an anti-reflectionfilm. For example, anti-glare treatment by which reflected light can bediffused by projections and depressions on the surface so as to reducethe glare can be performed.

The first electrode and the second electrode (each of which may becalled a pixel electrode, a common electrode, a counter electrode, orthe like) for applying voltage to the display element may havelight-transmitting properties or light-reflecting properties, whichdepends on the direction in which light is extracted, the position wherethe electrode is provided, and the pattern structure of the electrode.

The first electrode 930 and the second electrode 931 can be formed usinga light-transmitting conductive material such as indium oxide includingtungsten oxide, indium zinc oxide including tungsten oxide, indium oxideincluding titanium oxide, indium tin oxide including titanium oxide,indium tin oxide (hereinafter referred to as ITO), indium zinc oxide, orindium tin oxide to which silicon oxide is added.

Alternatively, the first electrode 930 and the second electrode 931 canbe formed using one or more materials selected from metals such astungsten (W), molybdenum (Mo), zirconium (Zr), hafnium (Hf), vanadium(V), niobium (Nb), tantalum (Ta), chromium (Cr), cobalt (Co), nickel(Ni), titanium (Ti), platinum (Pt), aluminum (Al), copper (Cu), andsilver (Ag); an alloy of any of these metals; and a nitride of any ofthese metals.

The first electrode 930 and the second electrode 931 can be formed usinga conductive composition including a conductive macromolecule (alsoreferred to as a conductive polymer). As the conductive high molecule,what is called a π-electron conjugated conductive polymer can be used.For example, polyaniline or a derivative thereof, polypyrrole or aderivative thereof, polythiophene or a derivative thereof, a copolymerof two or more of aniline, pyrrole, and thiophene or a derivativethereof, and the like can be given.

Since the transistor is easily broken owing to static electricity or thelike, a protective circuit for protecting the driver circuit ispreferred to be provided. The protection circuit is preferred to beformed using a nonlinear element.

As described above, by using any of the transistors described in theabove embodiments, a highly reliable semiconductor device having adisplay function can be provided.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 6

In this embodiment, a display device (also referred to as a touch panel)provided with a touch sensor (a contact detection device) is describedbelow.

FIG. 16 is a top view illustrating a structural example of a pixelportion of a display device 900. FIG. 17 is a cross-sectional view takenalong dashed-dotted line O-P in FIG. 16. Note that in FIG. 16, somecomponents are not illustrated for clarity. Further, in this embodiment,the reference numerals used in Embodiment 5 are used as appropriate.

The pixel portion includes at least the transistor 910, a scan line partof which functions as a gate electrode 972, a signal line part of whichfunctions as one electrode 974 of a pair of electrodes 974 and 975, thefirst electrode 930, the second electrode 931, and the spacer 935 (seeFIG. 16).

The transistor 910 includes the gate electrode 972, a gate insulatingfilm 976, the multilayer film 926, the pair of electrodes 974 and 975,and the insulating film 924. The gate electrode 972 is provided over theinsulating film 923 serving as a base film over the first substrate 901.The gate insulating film 976 is provided over the gate electrode 972,the multilayer film 926 is provided over the gate insulating film 976 tooverlap with the gate electrode 972, the pair of electrodes 974 and 975is provided over the multilayer film 926, and the insulating film 924 isprovided over the multilayer film 926 and the pair of electrodes 974 and975 (see FIG. 17).

Further, an organic resin film 945 is provided over the insulating film924. The second electrode 931 serving as a common electrode is providedover the organic resin film 945. An insulating film 937 is provided overthe organic resin film 945 and the second electrode 931. An openingreaching the electrode 975 is formed in the insulating film 924, theinsulating film 937, and the organic resin film 945, and the firstelectrode 930 serving as a pixel electrode is provided in the openingand over the insulating film 937 (see FIG. 17). That is, the firstelectrode 930 serving as a pixel electrode is electrically connected toone of the pair of electrodes 974 and 975.

Further, the insulating film 932 serving as an alignment film isprovided over the insulating film 937 and the first electrode 930serving as a pixel electrode. The insulating film 933 serving as analignment film is provided on a surface of the second substrate 906,which faces the first substrate 901, and the liquid crystal layer 908 isprovided between the insulating film 932 and the insulating film 933serving as alignment films. In addition to the above components, anoptical member may be provided as appropriate. For example, apolarization plate can be provided on the outer side of each of thefirst substrate 901 and the second substrate 906.

The display device 900 includes a capacitive sensor as a touch sensor.An electrode 941 is provided on the outer side of the second substrate906. Note that the polarization plate provided on the outer side of thesecond substrate 906 is provided between the electrode 941 and thesecond substrate 906.

The second electrode 931 which is on the first substrate 901 side andserves as a common electrode serves as a common electrode of a pixel andone electrode of a capacitor of a touch sensor. The electrode 941functions as the other electrode of the capacitor of the touch sensor.Further, a pixel portion of the display device 900 applies a pixelstructure of the FFS mode; thus, a conductive film is not formed on thesecond substrate 906 side, so that the electrode 941 functions as aconductor for preventing the second substrate 906 from being chargedwith electricity.

The transistor 910 can be formed using a material and a method similarto those of the transistor 50 described in Embodiment 1. That is, thegate electrode 972, the gate insulating film 976, the multilayer film926, the pair of electrodes 974 and 975, and the insulating film 924 canbe formed using a material and a method similar to those of the gateelectrode 15, the gate insulating film 17, the multilayer film 20, thepair of electrodes 21 and 22, and the protective film 26, respectively,of the transistor 50 described in Embodiment 1.

Further, one of or both the signal line driver circuit and the scan linedriver circuit of the display device 900 can be formed by using amanufacturing process of the transistor 910. For example, a transistorand a diode which are included in one of or both the signal line drivercircuit and the scan line driver circuit, and a lead wiring provided ina terminal portion connected to an FPC and the like, can be formed.

The organic resin film 945 can be formed using a material and a methodapplicable to the planarization film 921 or the partition wall 960 whichare described in Embodiment 5. The insulating film 937 can be formedusing a material and a method applicable to an insulating film (such asthe gate insulating film 976 and the insulating film 924) included inthe transistor 910.

One electrode 975 of the pair of electrodes 974 and 975 is in contactwith the first electrode 930 serving as a pixel electrode through theopening formed in the insulating film 924, the insulating film 937, andthe organic resin film 945. The opening can be formed by forming aresist mask through a photolithography process or the like and etchingthe insulating film 937 and the organic resin film 945 with the use ofthe resist mask. Specifically, the opening is formed through an etchingprocess of part of the insulating film 924 and part of the organic resinfilm 945 and an etching process of part of the insulating film 937.

FIG. 18A shows a cross-sectional view of one example of a connectionstructure in which the second electrode 931 serving as a commonelectrode is connected to a wiring 977 which is electrically connectedto the pair of electrodes 974 and 975. The wiring 977 is in contact withthe second electrode 931 serving as a common electrode through anopening formed in the insulating film 924 and the organic resin film945. With such a structure, potential can be supplied to the secondelectrode 931 serving as a common electrode by supplying potential tothe wiring 977. Note that the wiring 977 can be formed by using amanufacturing process of the pair of electrodes 974 and 975.

FIG. 18B shows a cross-sectional view of one example of a connectionstructure of a wiring in a terminal portion connected to an FPC and thelike. An electrode 979 is in contact with the wiring 977 through anopening formed in the insulating film 924 and the organic resin film945, and is in contact with the wiring 978 through an opening formed inthe gate insulating film 976, the insulating film 924, and the organicresin film 945. With such a structure, potential can be supplied to thewiring 977 by supplying potential to the wiring 978. Note that thewiring 978 can be formed by using a manufacturing process of the gateelectrode 972.

As illustrated in FIG. 18B, the wiring 977 is connected to the wiring978 through the electrode 979, whereby the number of photomasks can bereduced by one as compared to the case where a connection portion inwhich the wiring 977 is directly in contact with the wiring 978 isformed. It is because, in order to have a connection structure in whichthe wiring 977 is directly in contact with the wiring 978, a photomaskfor forming a contact hole in the gate insulating film 976 is neededbefore the pair of electrodes 974 and 975 is formed; however, thephotomask is not needed for the connection structure in FIG. 18B.

Further, instead of the transistor 910 illustrated in FIG. 17, atransistor 912 illustrated in FIG. 19 is formed using a multi-tone mask,whereby the number of photomasks can be reduced. The multi-tone mask isa mask capable of light exposure with multi-level light intensity, andtypically, light exposure is performed with three levels of lightintensity to provide an exposed region, a half-exposed region, and anunexposed region. By one light exposure and development step with theuse of the multi-tone mask, a resist mask with plural thicknesses(typically, two kinds of thicknesses) can be formed. Therefore, by theusage of the multi-tone mask, the number of photomasks can be reduced.Specifically, the multi-tone mask is used in a forming process of themultilayer film 927 and the pair of electrodes 928 and 929, whereby theone photomask can be cut. With the multi-tone mask, end portions of themultilayer film 927 are positioned on the outer side than end portionsof the pair of electrodes 928 and 929.

FIG. 20 is a plan view showing a structural example of the secondelectrode 931 serving as a common electrode and the electrode 941 whichare included in the display device 900. As illustrated in FIG. 20, thesecond electrode 931 serving as a common electrode and the electrode 941each have a stripe shape, and are provided so as to be perpendicular toeach other in a plane. Each second electrode 931 serving as a commonelectrode is connected to an FPC 954 attached to the substrate 901,through a lead wiring 951, and each electrode 941 is connected to an FPC955 attached to the substrate 906, through a lead wiring 952.

FIG. 21A is a cross-sectional view taken along dashed-dotted line Q-R inFIG. 20 and FIG. 21B is a plan view of a region 953 in FIG. 20. Asillustrated in FIG. 21A, the second electrode 931 serving as a commonelectrode is provided in common in a plurality of pixels, and the firstelectrode 930 serving as a pixel electrode is provided in each of thepixels and connected to the transistor 910. An electrostatic capacitorof a touch sensor is formed in a region where the second electrode 931serving as a common electrode and the electrode 941 intersect with eachother. The electrostatic capacitor is composed of the second electrode931 serving as a common electrode, the electrode 941, and a dielectricprovided between the second electrode 931 serving as a common electrodeand the electrode 941. The second electrode 931 serving as a commonelectrode is an electrode for supplying potential to the electrostaticcapacitor. The electrode 941 is an electrode for extracting currentflowing in the electrostatic capacitor.

An operation of the display device 900 can be roughly divided into adisplay operation in which an image signal is input to the pixel and asensing operation in which a touch is detected. In the displayoperation, potential of the second electrode 931 serving as a commonelectrode is fixed at a low level. In a sensing period, pulse signalsare sequentially applied to each second electrode 931 serving as acommon electrode and the potential is a high level. At this time, if afinger is touching the display device 900, a capacitance formed by thetouch with the finger is applied to the electrostatic capacitor of thetouch sensor; thus, current flowing in the capacitor is changed and thepotential of the electrode 941 is changed. The electrodes 941 aresequentially scanned and the change in the potential of the electrode941 is detected, whereby the location of the touch with the finger isdetected.

As described above, in a display device including a liquid crystalelement, as an electrode forming electrostatic capacity of the displaydevice 900, a common electrode of the pixel and the conductor forpreventing charge with electricity originally provided in a liquidcrystal device of the FFS mode can be used; thus, a touch panel that islight and thin and with a high display quality can be provided.

Here, the second electrode 931 serving as a common electrode is providedbelow the first electrode 930 serving as a pixel electrode (on the firstsubstrate 901 side); however, the second electrode 931 serving as acommon electrode can be provided over the first electrode 930 serving asa pixel electrode.

Note that as the structure of the display device, a structure except thedisplay device 900 described in this embodiment may be used. Forexample, an externally attached touch panel can be employed, in whichelectrostatic capacity is formed and a touch panel substrate is attachedto the first substrate 901 side or the second substrate 906 side of aliquid crystal display device or a light-emitting display device.Further, with a conductive film which is attached outside the firstsubstrate 901 or the second substrate 906 to prevent build-up of staticelectricity, a surface capacitive touch sensor can be formed.Hereinafter, a structural example of the touch sensor which is appliedto the externally attached touch panel is described with reference toFIGS. 22A to 22C and FIGS. 23A and 23B.

FIG. 22A is an exploded perspective view showing a structural example ofthe touch sensor, FIG. 22B is a plan view showing a structural exampleof an electrode 981 of the touch sensor, and FIG. 22C is a plan viewshowing a structural example of an electrode 982 of the touch sensor.

As illustrated in FIGS. 22A to 22C, in a touch sensor 980, a pluralityof electrodes 981 arranged in the X-axis direction and a plurality ofelectrodes 982 arranged in the Y-axis direction which intersects withthe X-axis direction are formed over a substrate 986.

The electrodes 981 and the electrodes 982 each have a structure in whicha plurality of quadrangular conductive films is connected to each other.The plurality of electrodes 981 and the plurality of electrodes 982 areeach provided so that the quadrangular conductive films are notoverlapped with each other. In a portion where the electrode 981 and theelectrode 982 intersect with each other, an insulating film is providedbetween the electrode 981 and the electrode 982 so that the electrode981 and the electrode 982 are not in contact with each other.

FIG. 23A is a cross-sectional view illustrating an example of connectionstructures of the electrode 981 and the electrode 982 and shows across-sectional view of a portion where the electrodes 981 and 982intersect with each other as an example. FIG. 23B is an equivalentcircuit diagram of the portion where the electrodes 981 and 982intersect with each other. As illustrated in FIG. 23B, in the portionwhere the electrodes 981 and 982 intersect with each other, a capacitor983 is formed.

As illustrated in FIG. 23A, in a sensor portion 989, the electrode 981includes a conductive film 981 a and a conductive film 981 b which arein the first layer, and a conductive film 981 c in the second layer overan insulating film 985. The conductive films 981 a and 981 b areconnected to each other via the conductive film 981 c. The electrode 982is formed using the conductive film in the first layer. An insulatingfilm 991 is formed to cover the electrode 981, the electrode 982, anelectrode 984, and the insulating film 985. As the insulating films 985and 991, for example, a silicon oxide film, a silicon oxynitride film,or the like may be used. Note that a base insulating film may be formedbetween the substrate 986 and each of the electrode 981 and theelectrode 984. As the base insulating film, for example, a silicon oxidefilm, a silicon oxynitride film, or the like can be used.

The electrodes 981 and 982 are formed using a conductive material havinga light-transmitting property with respect to visible light. Forexample, as the conductive material having a light-transmittingproperty, indium tin oxide containing silicon oxide, indium tin oxide,zinc oxide, indium zinc oxide, and zinc oxide to which gallium is addedare given.

The conductive film 981 a is connected to the electrode 984 in aterminal portion 990. A terminal for connecting to the FPC is formedusing the electrode 984. The electrode 982 is also connected to otherelectrode 984 like the electrode 981. The electrode 984 can be formedusing a tungsten film, for example.

An opening is formed in the insulating film 985 and the insulating film991 which are over the electrode 984 for electrically connecting theelectrode 984 and the FPC. A substrate 987 is attached to and over theinsulating film 991 using an adhesive, an adhesive film, or the like.The substrate 986 is attached to the first substrate 901 or the secondsubstrate 906 of the display device using an adhesive or an adhesivefilm, whereby a touch panel is formed.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 7

In this embodiment, a driving method for reducing power consumption of adisplay device is described. By using the driving method in thisembodiment, power consumption of a display device including an oxidesemiconductor transistor in a pixel can be further reduced. Withreference to FIGS. 24 and 25, low power consumption of a liquid crystaldisplay device, which is an example of the display device, is describedbelow.

FIG. 24 is a block diagram illustrating a structural example of a liquidcrystal display device in this embodiment. As shown in FIG. 24, a liquidcrystal display device 500 includes a liquid crystal panel 501 as adisplay module, a control circuit 510, and a counter circuit.

An image signal (Video), which is digital data, and a synchronizationsignal (SYNC) for controlling rewriting of a screen of the liquidcrystal panel 501 are input to the liquid crystal display device 500.Examples of a synchronization signal include a horizontalsynchronization signal (Hsync), a vertical synchronization signal(Vsync), and a reference clock signal (CLK).

The liquid crystal panel 501 includes a display portion 530, a scan linedriver circuit 540, and a data line driver circuit 550. The displayportion 530 includes a plurality of pixels 531. The pixels 531 in thesame row are connected to the scan line driver circuit 540 through acommon scan line 541, and the pixels 531 in the same column areconnected to the data line driver circuit 550 through a common data line551.

A high power supply voltage (VDD) and a low power supply voltage (VSS),which serve as power supply voltages, and a common voltage (hereinafterreferred to as Vcom) are supplied to the liquid crystal panel 501. Thecommon voltage (Vcom) is supplied to each pixel 531 in the displayportion 530.

The data line driver circuit 550 processes an input image signal togenerate a data signal, and outputs the data signal to the data line551. The scan line driver circuit 540 outputs, to the scan line 541, ascan signal for selecting the pixel 531 into which a data signal is tobe written.

The pixel 531 includes a switching element whose electrical connectionto the data line 551 is controlled by a scan signal. When the switchingelement is turned on, a data signal is written into the pixel 531through the data line 551.

An electrode to which Vcom is applied corresponds to a common electrode.

The control circuit 510 controls the whole liquid crystal display device500 and includes a circuit which generates control signals for circuitsincluded in the liquid crystal display device 500.

The control circuit 510 includes a control signal generation circuitwhich generates control signals for the scan line driver circuit 540 andthe data line driver circuit 550 on the basis of the synchronizationsignal (SYNC). Examples of a control signal for the scan line drivercircuit 540 include a start pulse (GSP) and a clock signal (GCLK).Examples of a control signal for the data line driver circuit 550include a start pulse (SSP) and a clock signal (SCLK). For example, thecontrol circuit 510 generates a plurality of clock signals with the samecycle and shifted phases as the clock signals (GCLK and SCLK).

Further, the control circuit 510 controls output of an image signal(Video), which is input from the outside of the liquid crystal displaydevice 500, to the data line driver circuit 550.

The data line driver circuit 550 includes a digital/analog conversioncircuit (hereinafter referred to as a D-A conversion circuit 552). TheD-A conversion circuit 552 converts an image signal to an analog signal,thereby generating a data signal.

Note that in the case where an image signal input to the liquid crystaldisplay device 500 is an analog signal, the image signal is converted toa digital signal in the control circuit 510 and output to the liquidcrystal panel 501.

An image signal is image data for each frame. The control circuit 510has a function of performing image processing on the image signal andcontrolling output of the image signal to the data line driver circuit550 on the basis of data obtained by the processing. For that function,the control circuit 510 includes a motion detection portion 511 whichdetects motion in the image data for each frame. The control circuit 510stops output of an image signal to the data line driver circuit 550 whenthe motion detection portion 511 determines that there is no motion, andrestarts the output of an image signal when the motion detection portion511 determines that there is motion.

There is no particular limitation on the image processing for detectingmotion which is performed in the motion detection portion 511. Anexample of a method for detecting motion is to obtain difference datafrom image data for two consecutive frames. It can be determined whetherthere is motion or not from the obtained difference data. Anotherexample of the method is to detect a motion vector.

In addition, the liquid crystal display device 500 may be provided withan image signal correction circuit which corrects an input image signal.For example, an image signal is corrected such that a voltage higherthan a voltage corresponding to the gray scale of the image signal iswritten into the pixel 531. Such correction can shorten the responsetime of the liquid crystal element. A method in which the controlcircuit 510 is driven with an image signal corrected in this manner isreferred to as overdriving. In the case of performing high frame ratedriving in which the liquid crystal display device 500 is driven at anintegral multiple of the frame frequency of an image signal, image datafor interpolation between two frames or image data for performing blackdisplay between two frames may be generated in the control circuit 510.

Next, the operation of the liquid crystal display device 500 fordisplaying an image with motion, such as a moving image, and an imagewithout motion, such as a still image, is described with reference to atiming chart in FIG. 25. FIG. 25 shows the signal waveforms of avertical synchronization signal (Vsync) and a data signal (Vdata) outputto the data line 551 from the data line driver circuit 550.

FIG. 25 is a timing chart of the liquid crystal display device 500during 3m frame periods. Here, there is motion in image data in thefirst k frame periods and the last j frame periods and there is nomotion in image data in the other frame periods. Note that k and j areeach an integer greater than or equal to 1 and less than or equal tom−2.

In the first k frame periods, the motion detection portion 511determines that there is motion in image data for each frame. Thecontrol circuit 510 outputs data signals (Vdata) to the data line 551 onthe basis of the result of determination by the motion detection portion511.

The motion detection portion 511 performs image processing for detectingmotion and determines that there is no motion in image data for the(k+1)-th frame. Then, the control circuit 510 stops output of imagesignals (Video) to the data line driver circuit 550 in the (k+1)-thframe period on the basis of the result of determination by the motiondetection portion 511. Thus, output of the data signal (Vdata) from thedata line driver circuit 550 to the data line 551 is stopped. Further,the control circuit 510 stops the supply of control signals (e.g., astart pulse signal and a clock signal) to the scan line driver circuit540 and the data line driver circuit 550 in order to stop rewriting ofthe display portion 530. The control circuit 510 does not output animage signal to the data line driver circuit 550 nor output controlsignals to the scan line driver circuit 540 and the data line drivercircuit 550, thereby keeping rewriting of the display portion 530stopped, until the motion detection portion 511 determines that there ismotion in image data.

Note that, in this specification, “not to supply” a signal to a liquidcrystal panel means to apply voltage which is different from apredetermined voltage for operating a circuit to a wiring for supplyingthe signal, or to bring the wiring into an electrically floating state.

When rewriting of the display portion 530 is stopped, an electric fieldin one direction is kept applied to the liquid crystal element, whichmight lead to deterioration of liquid crystal in the liquid crystalelement. In the case where such a problem is likely to occur, it ispreferable that signals be supplied to the scan line driver circuit 540and the data line driver circuit 550 from the control circuit 510 anddata signals with an inverted polarity be written into the data line 551at predetermined timings to invert the direction of the electric fieldapplied to the liquid crystal element, regardless of the result ofdetermination by the motion detection portion 511.

Note that the polarity of a data signal input to the data line 551 isdetermined relative to Vcom. The polarity is positive when the voltageof the data signal is higher than Vcom, and is negative when the voltageof the data signal is lower than Vcom.

Specifically, as shown in FIG. 25, in the (m+1)-th frame period, thecontrol circuit 510 outputs control signals to the scan line drivercircuit 540 and the data line driver circuit 550 and outputs an imagesignal (Video) to the data line driver circuit 550. The data line drivercircuit 550 outputs, to the data line 551, a data signal (Vdata) whichhas an inverted polarity with respect to a data signal (Vdata) output tothe data line 551 in the k-th frame period. In this manner, a datasignal (Vdata) with an inverted polarity is written into the data line551 in the (m+1)-th frame period and in the (2 m+1)-th frame period,which are periods in which no motion is detected in image data.Rewriting of the display portion 530 is intermittently performed inperiods in which there is no change in image data; thus, it is possibleto reduce power consumption due to rewriting and prevent deteriorationof the liquid crystal element.

When the motion detection portion 511 determines that there is motion inimage data for any frame after the (2m+1)-th frame, the control circuit510 controls the scan line driver circuit 540 and the data line drivercircuit 550 to perform rewriting of the display portion 530.

As described above, with the driving method in FIG. 25, the polarity ofa data signal (Vdata) is inverted every m frame periods regardless ofwhether there is motion in image data (Video) or not. Meanwhile, thedisplay portion 530 is rewritten every frame in periods in which animage with motion is displayed and is rewritten every m frames inperiods in which an image without motion is displayed. Consequently,power consumed owing to rewriting of the display portion can be reduced.This can prevent an increase in power consumption due to an increase indriving frequency and the number of pixels.

As described above, in the liquid crystal display device 500, the methodfor driving the liquid crystal display device is switched between in amoving image display mode and in a still image display mode; thus, it ispossible to provide a liquid crystal display device with low powerconsumption while inhibiting deterioration of liquid crystal andmaintaining display quality.

In the case where a still image is displayed, when a pixel is rewrittenevery one frame, human eyes perceive the rewriting of the pixel asflickers in some cases, which causes eyestrain. The pixel is notfrequently rewritten in the display period of the still image in theliquid crystal device of this embodiment, which is effective forreducing eyestrain.

Thus, with the use of a liquid crystal panel in which a backplane isformed using an oxide semiconductor transistor, a middle size liquidcrystal display device with high resolution and low power consumption,which is very suitable for a portable electronic device, can beprovided.

Note that, in order to prevent deterioration of the liquid crystal, theinterval between polarity inversions of data signals (here, m frameperiods) is set to two seconds or shorter, preferably one second orshorter.

Although the detection of motion in image data is performed in themotion detection portion 511 in the control circuit 510, the detectionof motion is not necessarily performed only in the motion detectionportion 511. Data on whether there is motion or not may be input to thecontrol circuit 510 from the outside of the liquid crystal displaydevice 500.

Determination that there is no motion in image data is not always basedon image data for two consecutive frames; the number of frames requiredfor the determination may be set as appropriate depending on the usagemode of the liquid crystal display device 500. For example, rewriting ofthe display portion 530 may be stopped when there is no motion in imagedata for m consecutive frames.

Note that although description of this embodiment is made using a liquidcrystal display device as a display device, the driving method in thisembodiment can be used for other display devices, e.g., a light-emittingdisplay device.

Note that the structures, methods, and the like described in thisembodiment can be used as appropriate in combination with any of thestructures, methods, and the like described in the other embodiments andexamples.

Embodiment 8

The semiconductor device which is one embodiment of the presentinvention can be applied to a variety of electronic appliances(including game machines). Examples of electronic appliances include atelevision device (also referred to as television or televisionreceiver), a monitor of a computer or the like, a digital camera, adigital video camera, a digital photo frame, a mobile phone, a portablegame machine, a portable information terminal, an audio reproducingdevice, a game machine (e.g., a pachinko machine or a slot machine), anda game console, and the like. Examples of these electronic appliancesare illustrated in FIGS. 26A to 26C.

FIG. 26A illustrates a table 9000 having a display portion. In the table9000, a display portion 9003 is incorporated in a housing 9001 and animage can be displayed on the display portion 9003. The housing 9001 issupported by four leg portions 9002. Further, a power cord 9005 forsupplying power is provided for the housing 9001.

The semiconductor device described in any of the above embodiments canbe used for the display portion 9003. Thus, the display portion 9003 canhave high display quality.

The display portion 9003 has a touch-input function. When a user touchesdisplayed buttons 9004 which are displayed on the display portion 9003of the table 9000 with his/her fingers or the like, the user can carryout operation of the screen and input of information. Further, when thetable may be made to communicate with home appliances or control thehome appliances, the display portion 9003 may function as a controldevice which controls the home appliances by operation on the screen.For example, with the use of the semiconductor device having an imagesensor function, the display portion 9003 can have a touch-inputfunction.

Further, the screen of the display portion 9003 can be placedperpendicular to a floor with a hinge provided for the housing 9001;thus, the table 9000 can also be used as a television device. When atelevision device having a large screen is set in a small room, an openspace is reduced; however, when a display portion is incorporated in atable, a space in the room can be efficiently used.

FIG. 26B illustrates a television device 9100. In the television device9100, a display portion 9103 is incorporated in a housing 9101 and animage can be displayed on the display portion 9103. Note that thehousing 9101 is supported by a stand 9105 here.

The television device 9100 can be operated with an operation switch ofthe housing 9101 or a separate remote controller 9110. Channels andvolume can be controlled with an operation key 9109 of the remotecontroller 9110 so that an image displayed on the display portion 9103can be controlled. Furthermore, the remote controller 9110 may beprovided with a display portion 9107 for displaying data output from theremote controller 9110.

The television device 9100 illustrated in FIG. 26B is provided with areceiver, a modem, and the like. With the receiver, general televisionbroadcasts can be received in the television device 9100. Further, whenthe television device 9100 is connected to a communication network bywired or wireless connection via the modem, one-way (from a transmitterto a receiver) or two-way (between a transmitter and a receiver orbetween receivers) data communication can be performed.

Any of the semiconductor devices described in the above embodiments canbe used for the display portions 9103 and 9107. Thus, the televisiondevice can have high display quality.

FIG. 26C illustrates a computer 9200, which includes a main body 9201, ahousing 9202, a display portion 9203, a keyboard 9204, an externalconnection port 9205, a pointing device 9206, and the like.

Any of the semiconductor devices described in the above embodiments canbe used for the display portion 9203. Thus, the computer 9200 can havehigh display quality.

The display portion 9203 has a touch-input function. When a user touchesdisplayed buttons which are displayed on the display portion 9203 of thecomputer 9200 with his/her fingers or the like, the user can carry outoperation of the screen and input of information. Further, when thetable may be made to communicate with home appliances or control thehome appliances, the display portion 9203 may function as a controldevice which controls the home appliances by operation on the screen.

FIGS. 27A and 27B illustrate a foldable tablet terminal. In FIG. 27A,the tablet terminal is opened and includes a housing 9630, a displayportion 9631 a, a display portion 9631 b, a display-mode switchingbutton 9034, a power button 9035, a power-saving-mode switching button9036, a clip 9033, and an operation button 9038.

Any of the semiconductor devices described in the above embodiments canbe used for the display portion 9631 a and the display portion 9631 b.Thus, the display quality of the tablet terminal can be improved.

Part of the display portion 9631 a can be a touch panel region 9632 aand data can be input when a displayed operation key 9638 is touched.Although a structure in which a half region in the display portion 9631a has only a display function and the other half region also has a touchpanel function is illustrated as an example, the structure of thedisplay portion 9631 a is not limited thereto. The whole area of thedisplay portion 9631 a may have a touch screen function. For example,the while area of the display portion 9631 a can display keyboardbuttons and serve as a touch screen while the display portion 9631 b canbe used as a display screen.

Like the display portion 9631 a, part of the display portion 9631 b canbe a touch screen region 9632 b. When a keyboard display switchingbutton 9639 displayed on the touch panel is touched with a finger, astylus, or the like, a keyboard can be displayed on the display portion9631 b.

Touch input can be performed concurrently on the touch screen regions9632 a and 9632 b.

The display-mode switching button 9034 can switch display orientation(e.g., between landscape mode and portrait mode) and select a displaymode (switch between monochrome display and color display), for example.The power-saving-mode switching button 9036 can control displayluminance in accordance with the amount of external light in use of thetablet terminal detected by an optical sensor incorporated in thetablet. The tablet terminal may include another detection device such asa sensor for detecting orientation (e.g., a gyroscope or an accelerationsensor) in addition to the optical sensor.

Although the display portion 9631 a and the display portion 9631 b havethe same display area in FIG. 27A, one embodiment of the presentinvention is not limited to this example. The display portion 9631 a andthe display portion 9631 b may have different areas or different displayquality. For example, one of them may be a display panel that candisplay higher-definition images than the other.

In FIG. 27B, the tablet terminal is folded and includes the housing9630, a solar cell 9633, and a charge and discharge control circuit9634. Note that in FIG. 27B, an example in which the charge anddischarge control circuit 9634 includes the battery 9635 and the DCDCconverter 9636 is illustrated.

Since the tablet can be folded in two, the housing 9630 can be closedwhen not in use. Thus, the display portions 9631 a and 9631 b can beprotected, thereby providing a tablet with high endurance and highreliability for long-term use.

In addition, the tablet terminal illustrated in FIGS. 27A and 27B canhave a function of displaying various kinds of data (e.g., a stillimage, a moving image, and a text image), a function of displaying acalendar, a date, the time, or the like on the display portion, atouch-input function of operating or editing the data displayed on thedisplay portion by touch input, a function of controlling processing bya variety of kinds of software (programs), and the like.

The solar cell 9633, which is attached on the surface of the tabletterminal, supplies electric power to a touch screen, a display portion,an image signal processor, and the like. Note that the solar cell 9633can be provided on one or both surfaces of the housing 9630, so that thebattery 9635 can be charged efficiently. The use of a lithium ionbattery as the battery 9635 is advantageous in downsizing or the like.

The structure and operation of the charge and discharge control circuit9634 illustrated in FIG. 27B are described with reference to a blockdiagram of FIG. 27C. The solar cell 9633, the battery 9635, the DCDCconverter 9636, a converter 9637, switches SW1 to SW3, and the displayportion 9631 are shown in FIG. 27C, and the battery 9635, the DCDCconverter 9636, the converter 9637, and the switches SW1 to SW3correspond to the charge/discharge control circuit 9634 in FIG. 27B.

First, an example of the operation in the case where power is generatedby the solar cell 9633 using external light is described. The voltage ofpower generated by the solar battery is raised or lowered by the DCDCconverter 9636 so that the power has a voltage for charging the battery9635. Then, when the power from the solar cell 9633 is used for theoperation of the display portion 9631, the switch SW1 is turned on andthe voltage of the power is raised or lowered by the converter 9637 soas to be a voltage needed for the display portion 9631. In addition,when display on the display portion 9631 is not performed, the switchSW1 is turned off and a switch SW2 is turned on so that charge of thebattery 9635 may be performed.

Note that the solar cell 9633 is described as an example of a powergeneration means; however, without limitation thereon, the battery 9635may be charged using another power generation means such as apiezoelectric element or a thermoelectric conversion element (Peltierelement). For example, the battery 9635 may be charged with anon-contact power transmission module that transmits and receives powerwirelessly (without contact) to charge the battery or with a combinationof other charging means.

Note that the structures and the like described in this embodiment canbe combined as appropriate with any of the structures and the likedescribed in the other embodiments.

Example 1

In this example, measurement results of Vg-Id characteristics and a BTphotostress test of a transistor are described.

First of all, a manufacturing process of a transistor included in Sample1 is described. In this example, the process is described with referenceto FIGS. 4A to 4D.

First, as illustrated in FIG. 4A, a glass substrate was used as thesubstrate 11, and the gate electrode 15 was formed over the substrate11.

A 100-nm-thick tungsten film was formed by a sputtering method, a maskwas formed over the tungsten film by a photolithography process, andpart of the tungsten film was etched with the use of the mask, so thatthe gate electrode 15 was formed.

Next, the gate insulating film 17 was formed over the gate electrode 15.

The gate insulating film 17 was formed by stacking a 50-nm-thick firstsilicon nitride film, a 300-nm-thick second silicon nitride film, a50-nm-thick third silicon nitride film, and a 50-nm-thick siliconoxynitride film.

The first silicon nitride film was formed under the followingconditions: silane with a flow rate of 200 sccm, nitrogen with a flowrate of 2000 sccm, and ammonia with a flow rate of 100 sccm weresupplied to a treatment chamber of a plasma CVD apparatus as the sourcegas; the pressure in the treatment chamber was controlled to 100 Pa, andthe power of 2000 W was supplied with the use of a 27.12 MHzhigh-frequency power source.

Next, the second silicon nitride film was formed under the conditionswhich are different from the conditions of the source gas of the firstsilicon nitride film in that the flow rate of ammonia was 2000 sccm.

Next, the third silicon nitride film was formed under the followingconditions: silane with a flow rate of 200 sccm and nitrogen with a flowrate of 5000 sccm were supplied to the treatment chamber of the plasmaCVD apparatus as the source gas; the pressure in the treatment chamberwas controlled to 100 Pa, and the power of 2000 W was supplied with theuse of a 27.12 MHz high-frequency power source.

Next, the silicon oxynitride film was formed under the followingconditions: silane with a flow rate of 20 sccm and dinitrogen monoxidewith a flow rate of 3000 sccm were supplied to the treatment chamber ofthe plasma CVD apparatus as the source gas; the pressure in thetreatment chamber was controlled to 40 Pa, and the power of 100 W wassupplied with the use of a 27.12 MHz high-frequency power source.

In each of the forming processes of the first to third silicon nitridefilms and the silicon oxynitride film, the substrate temperature was350° C.

Next, the multilayer film 20 overlapping with the gate electrode 15 withthe gate insulating film 17 provided therebetween was formed.

Here, a 35-nm-thick oxide semiconductor film was formed over the gateinsulating film 17 by a sputtering method, and then, a 20-nm-thick oxidefilm containing In or Ga was formed over the oxide semiconductor film.Next, a mask was formed over the oxide film containing In or Ga by aphotolithography process, and the oxide semiconductor film and the oxidefilm containing In or Ga were partly etched using the mask to form theoxide semiconductor film 18 and the oxide film 19 containing In or Ga,and then, heat treatment was performed; thus, the multilayer film 20 wasformed.

The oxide semiconductor film was formed under the following conditions:a sputtering target where In:Ga:Zn=1:1:1 (atomic ratio) was used; argonwith a flow rate of 50 sccm and oxygen with a flow rate of 50 sccm weresupplied as a sputtering gas into a treatment chamber of a sputteringapparatus; the pressure in the treatment chamber was controlled to 0.6Pa; and a direct-current power of 5 kW was supplied. Note that the oxidesemiconductor film was formed at a substrate temperature of 170° C.

The oxide film containing In or Ga was formed under the followingconditions: a sputtering target where In:Ga:Zn=1:3:2 (atomic ratio) wasused; argon with a flow rate of 90 sccm and oxygen with a flow rate of10 sccm were supplied as a sputtering gas into the treatment chamber ofthe sputtering apparatus; the pressure in the treatment chamber wascontrolled to 0.3 Pa; and a direct-current power of 5 kW was supplied.Note that the oxide film containing In or Ga was formed at a substratetemperature of 25° C.

As the heat treatment, heat treatment was performed at 450° C. in anitrogen atmosphere for one hour, and then, heat treatment was performedat 450° C. in an atmosphere of nitrogen and oxygen for one hour.

FIG. 4B can be referred to for the structure obtained through the stepsup to here.

Next, after the gate electrode was exposed by partly etching the gateinsulating film 17 (this step is not illustrated), the pair ofelectrodes 21 and 22 in contact with the multilayer film 20 was formedas illustrated in FIG. 4C.

Here, a conductive film was formed over the gate insulating film 17 andthe multilayer film 20. As the conductive film, a 400-nm-thick aluminumfilm was formed over a 50-nm-thick tungsten film, and a 100-nm-thicktitanium film was formed over the aluminum film. Then, a mask was formedover the conductive film by a photolithography process, and part of theconductive film was etched with the use of the mask, whereby the pair ofelectrodes 21 and 22 was formed.

Next, after the substrate was moved to a treatment chamber under reducedpressure and heated at 220° C., the substrate was moved to a treatmentchamber filled with dinitrogen monoxide. Then, the multilayer film 20was exposed to oxygen plasma which was generated by decomposition ofdinitrogen monoxide in such a manner that an upper electrode provided inthe treatment chamber was supplied with high-frequency power of 150 Wwith the use of a 27.12 MHz high-frequency power source.

Next, the protective film 26 was formed over the multilayer film 20 andthe pair of electrodes 21 and 22 (see FIG. 4D). Here, as the protectivefilm 26, the oxide insulating film 23, the oxide insulating film 24, andthe nitride insulating film 25 were formed.

First, after the above plasma treatment, the oxide insulating film 23and the oxide insulating film 24 were formed in succession withoutexposure to the atmosphere. A 50-nm-thick silicon oxynitride film wasformed as the oxide insulating film 23, and a 400-nm-thick siliconoxynitride film was formed as the oxide insulating film 24.

The oxide insulating film 23 was formed by a plasma CVD method under thefollowing conditions: silane with a flow rate of 30 sccm and dinitrogenmonoxide with a flow rate of 4000 sccm were used as source gases, thepressure in the treatment chamber was 200 Pa, the substrate temperaturewas 220° C., and the high-frequency power of 150 W was supplied toparallel plate electrodes.

The oxide insulating film 24 was formed by a plasma CVD method under thefollowing conditions: silane with a flow rate of 200 sccm and dinitrogenmonoxide with a flow rate of 4000 sccm were used as source gases, thepressure in the treatment chamber was 200 Pa, the substrate temperaturewas 220° C., and the high-frequency power of 1500 W was supplied toparallel plate electrodes. Under the above conditions, it is possible toform a silicon oxynitride film containing oxygen at a higher proportionthan oxygen in the stoichiometric composition and from which part ofoxygen is released by heating.

Next, heat treatment was performed, whereby water, nitrogen, hydrogen,and the like were released from the oxide insulating film 23 and theoxide insulating film 24. Here, the heat treatment was performed in anatmosphere of nitrogen and oxygen at 350° C. for one hour.

Next, the substrate was transferred to a treatment chamber under reducedpressure and heated at 350° C., and the nitride insulating film 25 wasformed over the oxide insulating film 24. Here, as the nitrideinsulating film 25, a 100-nm-thick silicon nitride film was formed.

The nitride insulating film 25 was formed by a plasma CVD method underthe following conditions: silane with a flow rate of 50 sccm, nitrogenwith a flow rate of 5000 sccm, and ammonia with a flow rate of 100 sccmwere used as a source gas, the pressure in the treatment chamber was 100Pa, the substrate temperature was 350° C., and the high-frequency powerof 1000 W was supplied to parallel plate electrodes.

Next, although not illustrated, an opening which exposes part of thepair of electrodes 21 and 22 was formed by partly etching the protectivefilm 26.

Next, a planarization film was formed (not illustrated) over the nitrideinsulating film 25. Here, the nitride insulating film 25 was coated witha composition, and exposure and development were performed, so that aplanarization film having an opening through which the pair ofelectrodes is partly exposed was formed. Note that as the planarizationfilm, a 1.5-μm-thick acrylic resin was formed. Then, heat treatment wasperformed. The heat treatment was performed at a temperature of 250° C.in an atmosphere containing nitrogen for one hour.

Next, a conductive film connected to part of the pair of electrodes wasformed (not illustrated). Here, a 100-nm-thick ITO film containingsilicon oxide was formed by a sputtering method. After that, heattreatment was performed at 250° C. in a nitrogen atmosphere for onehour.

Through the above process, the Sample 1 including a transistor wasformed.

Further, a sample including a transistor manufactured such that, in thetransistor of Sample 1, the third silicon nitride film in the gateinsulating film 17 was formed under conditions similar to those of thefirst silicon nitride film and the oxide semiconductor film 18 and theoxide film 19 containing In or Ga are formed at a substrate temperatureof 200° C. was manufactured as Sample 2.

Further, a sample including a transistor which is different from thetransistor of the Sample 1 in that the oxide film 19 containing In or Gais not formed was formed as Sample 3. Note that after the pair ofelectrodes 21 and 22 was formed, a surface of the oxide semiconductorfilm 18 was subjected to cleaning treatment using a phosphoric acidsolution in which 85% phosphoric acid was diluted by 100 times.

Furthermore, a sample having a transistor without the oxide insulatingfilm 23 in Sample 3 was manufactured as Sample 4.

Next, initial Vg-Id characteristics of the transistors included inSample 1 to Sample 4 were measured. Here, change in characteristics ofcurrent flowing between a source electrode and a drain electrode(hereinafter referred to as the drain current), that is, Vg-Idcharacteristics were measured under the following conditions: thesubstrate temperature was 25° C., the potential difference between thesource electrode and the drain electrode (hereinafter referred to as thedrain voltage) was 1 V or 10 V, and the potential difference between thesource electrode and the gate electrode (hereinafter referred to as thegate voltage) were changed from −20 V to +15 V.

FIGS. 28A to 28D show Vg-Id characteristics of the transistors includedin the samples. In FIGS. 28A to 28D, the horizontal axis indicates thegate voltage Vg and the vertical axis indicates the drain current Id.Further, the solid lines indicate the Vg-Id characteristics at the drainvoltages Vd of 1 V and 10 V, and the dashed line indicates thefield-effect mobility with respect to the gate voltages at the drainvoltage Vd of 10 V. Note that the field-effect mobility was obtained byoperation of each sample in a saturation region.

Note that in each of the transistors, the channel length (L) is 6 μm andthe channel width (W) is 50 μm. Further, in each of the samples, 20transistors having the same structure were formed on the substrate.

According to FIG. 28D, in the Vg-Id characteristics of the transistorsincluded in Sample 4, gate voltage at which on-state current startsflowing (also referred to as rising gate voltage (Vg)) when a drainvoltage Vd is 1 V is different from rising gate voltage of the on-statecurrent when a drain voltage Vd is 10 V. Further, variation in the Vg-Idcharacteristics of the transistors included in Sample 4 is large. On theother hand, according to FIGS. 28A to 28C, in the Vg-Id characteristicsof the transistors included in Sample 1 and Sample 3, the rising gatevoltage (Vg) of the on-state current at the drain voltage Vd of 1 V andthe rising gate voltage (Vg) of the on-state current at the drainvoltage Vd of 10 V are substantially the same. Moreover, variation inthe Vg-Id characteristics of the transistors included in Sample 1 toSample 3 is small. Thus, by providing at least the oxide insulating film23 between the multilayer film 20 and the oxide insulating film 24, theinitial characteristics of the transistor are improved.

Next, a BT stress test and a BT photostress test were performed on eachof Sample 1 to Sample 4. Here, the BT stress test in which thepredetermined voltage was applied to the gate electrode was performedunder the following conditions: the substrate temperature was 80° C.,the intensity of an electric field applied to the gate insulating filmwas 0.66 MV/cm, and the application time was 2000 seconds. Note that theBT stress test was performed in an air atmosphere in which the dew-pointtemperature is 12° C.

Under conditions similar to those of the above BT stress test, the BTphotostress test in which the transistor is irradiated with white LEDlight with 3000 lx to apply the predetermined voltage to the gateelectrode was performed. Note that the BT photostress test was performedin a dry-air atmosphere in which the dew-point temperature is −30° C.

Here, a measurement method of the BT stress test is described. First, asdescribed above, initial Vg-Id characteristics of the transistor weremeasured.

Next, the substrate temperature was raised to 80° C., and then, thepotentials of the source electrode and the drain electrode of thetransistor were set to 0 V. Then, voltage was kept being applied to thegate electrode for 2000 seconds so that the intensity of the electricfield applied to the gate insulating film was 0.66 MV/cm.

Note that in a negative BT stress test (dark, −GBT), a voltage of −30 Vwas applied to the gate electrode, and in a positive BT stress test(dark, +GBT), a voltage of 30 V was applied to the gate electrode. In anegative BT photostress test (photo, −GBT), a voltage of −30 V wasapplied to the gate electrode while the transistor was irradiated withwhite LED light with 3000 lx. In a positive BT photostress test (photo,+GBT), a voltage of 30 V was applied to the gate electrode while thetransistor was irradiated with white LED light with 3000 lx.

Next, the substrate temperature was lowered to 25° C. while voltage wascontinuously applied to the gate electrode, and the source electrode andthe drain electrode. After the substrate temperature reached to 25° C.,the application of voltage to the gate electrode, and the sourceelectrode and the drain electrode was stopped.

Further, FIG. 29 shows, in Sample 1 to Sample 4, a difference between athreshold voltage in the initial characteristics of the transistors anda threshold voltage after BT stress tests (i.e., the amount of change ofthe threshold voltage (ΔVth)). FIG. 29 shows the amounts of change ofthe threshold voltage (ΔVth) in the positive BT stress test (dark,+GBT), the negative BT stress test (dark, −GBT), the positive BTphotostress test (photo, +GBT), and the negative BT photostress test(photo, −GBT).

Note that in this specification, threshold voltage is calculated with adrain voltage Vd of 10 V. Further, in this specification, thresholdvoltage (Vth) refers to an average value of Vth of 20 transistorsincluded in each sample.

Further, according to FIG. 29, it is found that the absolute value ofthe amount of change in the threshold voltage of the transistors inSample 1 and Sample 2 decreases compared to the absolute value of theamount of change in the threshold voltage (ΔVth) of the transistors inSample 3 and Sample 4. In particular, in Sample 1, the amount of changein the threshold voltage (ΔVth) due to the positive BT stress test(dark, +GBT) remarkably decreases. Thus, with at least the oxide film 19containing In or Ga provided between the oxide semiconductor film 18 andthe oxide insulating film 24, the reliability of the transistor can beimproved.

In this manner, with the oxide film 19 containing In or Ga and the oxideinsulating film 23 provided between the oxide semiconductor film 18 andthe oxide insulating film 24, the electrical characteristics of thetransistor can be improved. Specifically, both the initialcharacteristics and the reliability can be improved. Further, the oxidefilm 19 containing In or Ga and the oxide insulating film 23 can inhibitentry of elements (e.g., silicon and nitrogen) contained in the oxideinsulating film 24 into the oxide semiconductor film 18 which is achannel region. Furthermore, the oxide film 19 containing In or Ga andthe oxide insulating film 23 can inhibit the oxide semiconductor film 18which is a channel region from receiving plasma damage at the time offorming the oxide insulating film 24 by a plasma CVD method withrelatively high power density.

Example 2

In this example, the dependence of the transistors included in Sample 1of Example 1 on a temperature of the BT stress test is described.

Sample 1 of Example 1 was used, a temperature of the BT stress testperformed in Example 1 was set to 60° C. or 80° C., and the length oftime for which stress was applied was 3600 seconds.

Specifically, first, after Vg-Id characteristics as the initialcharacteristics of the transistors were measured in a manner similar tothat in Example 1, the substrate temperature was raised to 60° C. or 80°C., and then, the potentials of the source electrodes and the drainelectrodes of the transistors were set to 0 V. After that, voltage waskept being applied to the gate electrode for 3600 seconds so that theintensity of the electric field applied to the gate insulating film was0.66 MV/cm. Note that in a negative BT stress test (dark, −GBT), avoltage of −30 V was applied to the gate electrode, and in a positive BTstress test (dark, +GBT), a voltage of 30 V was applied to the gateelectrode.

Next, the substrate temperature was decreased to 25° C. while a voltagewas applied to the gate electrode and the source and drain electrodes.After the substrate temperature was reached to 25° C., the applicationof voltage to the gate electrode, and the source electrode and the drainelectrode was stopped.

The Vg-Id characteristics of the transistors included in Samples 1 afterBT stress tests at the above temperatures are shown in FIGS. 30A to 30D.The results concerning a positive BT stress test at a substratetemperature of 60° C. are shown in FIG. 30A, the results concerning anegative BT stress test at a substrate temperature of 60° C. are shownin FIG. 30B, the results concerning a positive BT stress test at asubstrate temperature of 80° C. are shown in FIG. 30C, and the resultsconcerning a negative BT stress test at a substrate temperature of 80°C. are shown in FIG. 30D. In FIGS. 30A to 30D, thick lines in the graphseach represent the Vg-Id characteristics (initial characteristics)before the BT stress test, and thin lines each represent the Vg-Idcharacteristics after the BT stress test. Further, thick dashed lineseach represent field-effect mobility before the BT stress test, and thindashed lines each represent field-effect mobility after the BT stresstest. Note that the Vg-Id characteristics as the initial characteristicsand the Vg-Id characteristics after the BT stress test at eachtemperature were measured with drain voltage set to 10 V.

Further, a difference between a threshold voltage in the initialcharacteristics of the transistors included in Sample 1 and a thresholdvoltage after the BT stress tests (i.e., the amount of change inthreshold voltage (ΔVth)) is shown in FIG. 31.

It can be determined from FIG. 31 that, at temperatures of 60° C. and80° C., the amount of change in threshold voltage at least after thepositive BT stress test is less than or equal to 1.0 V.

Example 3

In this example, change over time of threshold voltage of a transistorwhich is one embodiment of the present invention is described. Here, aBT stress test was performed on the transistor which is one embodimentof the present invention, and the results of evaluating the amount ofchange in threshold voltage (ΔVth) with respect to stress test aredescribed.

A sample subjected to a BT stress test is described. The samplesubjected to the BT stress test is a sample manufactured such that, inSample 1 described in Example 1, an In—Ga—Zn oxide film to be processedinto the oxide film 19 containing In or Ga of the multilayer film 20 wasformed at a substrate temperature of 100° C. This sample is referred toas Sample 5.

Further, as a comparative example of Sample 5, Sample 6 manufactured ina manner similar to that of Sample 3 of Example 1 was used.

In this example, in a method similar to the BT stress test described inExample 1, the substrate temperature was set to 60° C. or the substratetemperature was set to 125° C., and heating was maintained for 3600seconds. As for Sample 5, the amount of change in threshold voltageafter a lapse of 100 seconds, 500 seconds, 1500 seconds, 2000 seconds,and 3600 seconds in time in which heating was maintained was evaluated.As for Sample 6, the amount of change in threshold voltage after a lapseof 100 seconds, 600 seconds, and 3600 seconds in time in which heatingwas maintained was evaluated.

The amounts of change in threshold voltage of Sample 5 and Sample 6after each elapsed time are shown in FIGS. 32A and 32B. In FIGS. 32A and32B, circles indicate the measurement results of Sample 5, and trianglesindicate the measurement results of Sample 6. Note that the amount ofchange in threshold voltage when the substrate temperature is set at 60°C. is shown in FIG. 32A, and the amount of change in threshold voltagewhen the substrate temperature is set at 125° C. is shown in FIG. 32B.

Further, FIGS. 32A and 32B are graphs in each of which an approximateline up to 10,000 seconds was extrapolated on the basis of shift of theamount of change in threshold voltage. In FIG. 32A, the formula of theapproximate line of Sample 5 was y=0.0138x^(0.424) and a coefficientvalue of determination R² was 0.990. The formula of the approximate lineof Sample 6 was y=0.0492x^(0.427) and a coefficient value ofdetermination R² was 0.992. In FIG. 32B, the formula of the approximateline of Sample 5 was y=0.0206x^(0.506) and a coefficient value ofdetermination R² was 0.999. The formula of the approximate line ofSample 6 was y=0.1304x^(0.428) and a coefficient value of determinationR² was 0.997.

It can be determined from FIGS. 32A and 32B that, at each of thesubstrate temperature of 60° C. and the substrate temperature of 125°C., the amount of change in threshold voltage after each elapsed time ofthe transistor having the multilayer film 20 as in Sample 5 is smallerthan that of Sample 6.

It can be determined that, in the case where the substrate temperatureis 60° C., the amount of change in threshold voltage of Sample 5 is lessthan or equal to 1 V even after a lapse of 10000 seconds while theamount of change in threshold voltage of Sample 6 reaches 1 V inapproximately 1000 seconds.

Further, it has been determined that, in the case where the substratetemperature is 125° C., time in which the amount of change in thresholdvoltage of Sample 5 reaches 1 V is 20 or more times (approximately 30 orless times) that of Sample 6.

From the above, with the use of the multilayer film of the oxidesemiconductor film and the oxide film containing In or Ga as in thetransistor which is one embodiment of the present invention, atransistor with improved reliability can be manufactured.

Example 4

In this example, the relation between the formation conditions of theoxide insulating film 23 and the oxide insulating film 24 in any of theabove examples, the number of water molecules released from the oxideinsulating film 23, the number of oxygen molecules released from theoxide insulating film 24, and the number of defects generated in theoxide semiconductor film when the oxide insulating film 23 or the oxideinsulating film 24 is formed is described.

First, a sample was manufactured in which a 400-nm-thick siliconoxynitride film was formed over a silicon wafer by a plasma CVD methodas the oxide insulating film 23 or the oxide insulating film 24 undereach formation condition, and the sample was evaluated by TDSmeasurement.

First, the structures of evaluated samples are described. Sample 7 is asample in which a silicon oxynitride film was formed under the followingconditions. In the conditions, as source gases, the flow rate of silanewas set to 30 sccm, and the flow rate of dinitrogen monoxide was set to4000 sccm, the pressure in the treatment chamber was set to 200 Pa, thesubstrate temperature was set to 220° C., and a high-frequency power of150 W was supplied to parallel-plate electrodes. Note that Sample 7 is asilicon oxynitride film formed using the formation conditions of theoxide insulating film 23 in Sample 1 of Example 1.

Next, Sample 8 is a sample in which a silicon oxynitride filmcorresponding to the oxide insulating film 23 in any of the aboveexamples was formed under the following conditions. In the conditions,pressure in the treatment chamber was set to 120 Pa in the conditions ofSample 7.

Sample 9 is a sample in which a silicon oxynitride film corresponding tothe oxide insulating film 23 in any of the above examples was formedunder the following conditions. In the conditions, pressure in thetreatment chamber was set to 40 Pa in the conditions of Sample 7.

The results of TDS measurements of Sample 7 to Sample 9 are shown inFIGS. 33A to 33C. FIG. 33A shows measurement results indicating thenumber of water molecules released from Sample 7, FIG. 33B showsmeasurement results indicating the number of water molecules releasedfrom Sample 8, and FIG. 33C shows measurement results indicating thenumber of water molecules released from Sample 9. From FIGS. 33A to 33C,a peak at a substrate temperature of approximately 120° C. in Sample 9is higher than peaks in Sample 7 and Sample 8. That is, it can be foundthat the numbers of released water molecules of Sample 7 and Sample 8 ata substrate temperature lower than or equal to 300° C. are smaller thanthat of Sample 9.

Note that the total number of water molecules released by heatingcorresponds to a value of the integral of a curve showing the result ofTDS analysis. In Sample 7, the amount released by heating attemperatures ranging from 55° C. to 600° C. was 5.6×10¹⁶ molecules/cm².In Sample 8, the number released by heating at temperatures ranging from50° C. to 600° C. was 5.4×10¹⁶ molecules/cm². In Sample 9, the numberreleased by heating at temperatures ranging from 50° C. to 580° C. was6.5×10¹⁶ molecules/cm². Note that the value obtained by converting thenumber of water molecules released from Sample 7 into that per unitvolume was 1.4×10²¹ molecules/cm³, the value obtained by converting thenumber of water molecules released from Sample 8 into that per unitvolume was 1.3×10²¹ molecules/cm³, and the value obtained by convertingthe number of water molecules released from Sample 9 into that per unitvolume was 1.6×10²¹ molecules/cm³.

It can be found that, by increasing the pressure when the siliconoxynitride film which is the oxide insulating film 23 is formed, thenumber of water molecules released at a substrate temperature lower thanor equal to 300° C. can be reduced.

Next, as the oxide insulating film 24 of the transistor described in anyof the above examples, a silicon oxynitride film which contains moreoxygen than that in the stoichiometric composition and from which partof oxygen is released by heating is described.

In order to confirm that more oxygen than that in the stoichiometriccomposition is contained and part of oxygen is released by heating, TDSmeasurement was performed to measure the amount of released oxygen.

First, the structures of samples subjected to the measurement aredescribed. In Reference sample 1, a 400-nm-thick silicon oxynitride filmwas formed over a silicon wafer under the following conditions. In theconditions, formation was performed by a plasma CVD method in whichsilane with a flow rate of 160 sccm and dinitrogen monoxide with a flowrate of 4000 sccm were used as source gases, the pressure in a treatmentchamber was 200 Pa, the substrate temperature was 220° C., and ahigh-frequency power of 1500 W was supplied to parallel plateelectrodes.

Reference sample 2 is a reference sample in which a 400-nm-thick siliconoxynitride film was formed over a silicon wafer under the followingconditions. As the conditions, the flow rate of silane was changed into200 sccm in the conditions of Reference sample 1, and conditions exceptthat are the same as those of Reference sample 1.

The results of TDS measurements of Reference sample 1 and Referencesample 2 are shown in FIGS. 34A and 34B. In FIGS. 34A and 34B, a peak ofM/z=32 corresponding to the mass number of an oxygen molecule wasobserved from each of Reference sample 1 and Reference sample 2. Thus,as for the silicon oxynitride film in each of Reference sample 1 andReference sample 2, it can be said that part of oxygen moleculescontained in the film is released by heating.

Note that the total number of oxygen molecules released by heatingcorresponds to a value of the integral of a curve showing the result ofTDS analysis. In Reference sample 1, the amount released by heating attemperatures ranging from 60° C. to 575° C. was 3.2×10¹⁴ molecules/cm².In Reference sample 2, the number released by heating at temperaturesranging from 60° C. to 600° C. was 1.9×10¹⁴ molecules/cm². Note that thevalue obtained by converting the amount of oxygen released fromReference sample 1 into oxygen atoms (per unit volume) was 1.6×10¹⁹atoms/cm³, and the value obtained by converting the amount of oxygenreleased from Reference sample 2 into oxygen atoms (per unit volume) was9.5×10¹⁸ atoms/cm³.

From the above, when the flow rate of silane relative to dinitrogenmonoxide is increased, defects in a silicon oxynitride film formed canbe reduced, whereas the number of released oxygen molecules is reduced.Further, when the flow rate of silane relative to dinitrogen monoxide isreduced, the number of released oxygen molecules is found to beincreased.

Next, defects generated in an oxide semiconductor film when the oxideinsulating film 23 used in Sample 7 to Sample 9 or the oxide insulatingfilm 24 used in Reference sample 1 and Reference sample 2 is formed overthe oxide semiconductor film are described. In this example, the numberof defects in the oxide semiconductor film is described using theresults of electron spin resonance (ESR) measurement.

First, the structures of evaluated samples are described.

Sample 10 to Sample 12 and Reference sample 3 and Reference sample 4each include a 100-nm-thick oxide semiconductor film formed over aquartz substrate and a 400-nm-thick oxide insulating film formed overthe oxide semiconductor film.

The oxide semiconductor film was formed in such a manner that asputtering target where In:Ga:Zn=1:1:1 (atomic ratio) was used, argonwith a flow rate of 50 sccm and oxygen with a flow rate of 50 sccm weresupplied as sputtering gases into a treatment chamber of a sputteringapparatus, the pressure in the treatment chamber was adjusted to 0.6 Pa,and a direct-current power of 5 kW was supplied. Note that the oxidesemiconductor film was formed at a substrate temperature of 170° C.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Sample 7 is referred to as Sample 10.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Sample 8 is referred to as Sample 11.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Sample 9 is referred to as Sample 12.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Reference sample 1 is referred to as Reference sample3.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Reference sample 2 is referred to as Reference sample4.

That is, in each of Samples 10 to Sample 12, a silicon oxynitride filmcorresponding to the oxide insulating film 23 was formed. In addition,in Reference sample 3 and Reference sample 4, a silicon oxynitride filmcorresponding to the oxide insulating film 24 was formed.

Next, ESR measurement was performed on Sample 10 to Sample 12 andReference sample 3 and Reference sample 4. In the ESR measurementperformed at a predetermined temperature, a value of a magnetic field(H₀) where a microwave is absorbed is used for an equation g=hν/βH₀, sothat a parameter of a g-factor can be obtained. Note that ν representsthe frequency of the microwave. Note that h and β represent the Planckconstant and the Bohr magneton, respectively, and are both constants.

Here, the ESR measurement was performed under the following conditions.The measurement temperature was room temperature (25° C.), thehigh-frequency power (power of microwaves) of 9.06 GHz was 20 mW, andthe direction of a magnetic field was parallel to a film surface of eachsample.

The number of spins of signals that appear at g (g-factor)=1.93 is shownin FIG. 35.

It can be found that the numbers of spins in Sample 10 and Sample 11 aresmaller than that in Sample 12. That is, it can be found that damage tothe oxide semiconductor film is relieved when the pressure is higherthan or equal to 100 Pa and lower than or equal to 250 Pa in the filmformation conditions of the oxide insulating film 23.

In FIGS. 34A and 34B, in the film formation conditions of the oxideinsulating film 24 which contains more oxygen than that in thestoichiometric composition and from which part of oxygen is released byheating, when the flow rate of silane relative to dinitrogen monoxide isincreased as that of Reference sample 2, the number of released oxygenmolecules is reduced, though defects in the oxide insulating film 24 canbe reduced. However, in the film formation conditions of the oxideinsulating film 23, when the pressure is set to be higher than or equalto 100 Pa and lower than or equal to 250 Pa as set for Sample 10 andSample 11, damage to the oxide semiconductor film is relieved; thus,defects in the oxide semiconductor film can be sufficiently reduced evenwhen the amount of excess oxygen moved from the oxide insulating film 24from which part of oxygen is released by heating is small.

The results of TDS and ESR measurements in this example indicate that,when the pressure is set to be higher than or equal to 100 Pa and lowerthan or equal to 250 Pa in the film formation conditions of the oxideinsulating film 23 formed over the transistor, the number of watermolecules released from the oxide insulating film 23 can be reduced anddamage to the oxide semiconductor film can be reduced, so that thenumber of oxygen vacancies can be reduced. Thus, movement of water fromthe oxide insulating film 23 to the oxide semiconductor film can bereduced. Further, even when the number of oxygen molecules released fromthe oxide insulating film which contains more oxygen than that in thestoichiometric composition and from which part of oxygen is released byheating is small, the oxygen vacancies in the oxide semiconductor filmcan be sufficiently reduced. Therefore, when the pressure is set to behigher than or equal to 100 Pa and lower than or equal to 250 Pa in thefilm formation conditions of the oxide insulating film 23, theelectrical characteristics of the transistor can be improved.

Example 5

In this example, the defect density of the oxide insulating film 24 usedin Reference sample 1 and Reference sample 2 in Example 4 is described.In this example, the number of defects in the oxide insulating film 24is described using the results of ESR (electron spin resonance)measurement.

First, the structures of evaluated samples are described.

Reference sample 5 and Reference sample 6 each include a 100-nm-thickoxide semiconductor film formed over a quartz substrate and a400-nm-thick oxide insulating film formed over the oxide semiconductorfilm.

As in Reference sample 3 and Reference sample 4, the oxide semiconductorfilm was formed in such a manner that a sputtering target whereIn:Ga:Zn=1:1:1 (atomic ratio) was used, argon with a flow rate of 50sccm and oxygen with a flow rate of 50 sccm were supplied as sputteringgases into a treatment chamber of a sputtering apparatus, the pressurein the treatment chamber was adjusted to 0.6 Pa, and a direct-currentpower of 5 kW was supplied. Note that the oxide semiconductor film wasformed at a substrate temperature of 170° C.

Next, after heat treatment was performed at 450° C. under a nitrogenatmosphere for one hour, heat treatment was performed at 450° C. in anatmosphere of nitrogen and oxygen for one hour.

Next, an oxide insulating film was formed over the oxide semiconductorfilm. A sample including the oxide insulating film under conditionssimilar to those of the silicon oxynitride film in Reference sample 1 isreferred to as Reference sample 5.

A sample including the oxide insulating film formed over the oxidesemiconductor film under conditions similar to those of the siliconoxynitride film in Reference sample 2 is referred to as Reference sample6.

Next, Reference sample 5 and Reference sample 6 were measured by ESR.Here, the ESR measurement was performed under the following conditions.The measurement temperature was −170° C., the high-frequency power(power of microwaves) of 9.1 GHz was 1 mW, and the direction of amagnetic field was parallel to a surface of each sample.

The number of spins of signals which appear at g (g-factor)=2.001 due todangling bonds of silicon is shown in FIG. 36.

It can be found that the number of spins in Reference sample 6 issmaller than that in Reference sample 5. That is, in the film formationconditions of the oxide insulating film 24, when the flow rate of silaneis 200 sccm and the flow rate of dinitrogen monoxide is 4000 sccm, it ispossible to form a silicon oxynitride film with fewer defects,typically, a silicon oxynitride film in which the spin density of asignal which appears at g=2.001, is lower than 6×10¹⁷ spins/cm³,preferably lower than or equal to 3×10¹⁷ spins/cm³, more preferablylower than or equal to 1.5×10¹⁷ spins/cm³ by ESR measurement.

Example 6

In this example, a localized state of a multilayer film included in atransistor which is one embodiment of the present invention isdescribed. Here, the results of evaluating the multilayer film by CPMmeasurement are described.

First, samples subjected to CPM measurement are described.

A 30-nm-thick first oxide film containing In or Ga was formed over aglass substrate, a 100-nm-thick oxide semiconductor film was formed overthe first oxide film containing In or Ga, and a 30-nm-thick second oxidefilm containing In or Ga was formed over the oxide semiconductor film;thus, the multilayer film was formed.

In this example, the first oxide film containing In or Ga and the secondoxide film containing In or Ga are oxide films each formed by asputtering method using an In—Ga—Zn oxide (In:Ga:Zn=1:3:2 [atomicratio]) target. Note that the films were formed in such a manner that anargon gas of 30 sccm and an oxygen gas of 15 sccm were used as a filmformation gas, the pressure was set to be 0.4 Pa, the substratetemperature was set to be 200° C., and a DC power of 0.5 kW was applied.

Further, the oxide semiconductor film is an oxide semiconductor filmformed by a sputtering method using an In—Ga—Zn oxide (In:Ga:Zn=1:1:1[atomic ratio]) target. Note that the film was formed in such a mannerthat an argon gas of 30 sccm and an oxygen gas of 15 sccm were used as adeposition gas, the pressure was set to be 0.4 Pa, the substratetemperature was set to be 200° C., and a DC power of 0.5 kW was applied.

A sample manufactured in the above-described manner is referred to asSample 13.

Next, CPM measurement was performed on Sample 13. Specifically, theamount of light with which a surface of Sample 13 between terminals isirradiated is adjusted so that a photocurrent value is kept constant inthe state where voltage is applied between a first electrode and asecond electrode provided in contact with the multilayer film of thesample, and then an absorption coefficient is derived from the amount ofthe irradiation light in an intended wavelength range.

FIGS. 37A and 37B shows results of fitting the absorption coefficient(thick dotted line) measured using a spectrophotometer and theabsorption coefficient (thick solid line) measured by CPM in the rangeof energy higher than or equal to the energy gap of each layer includedin the multilayer film. Note that in a curve of the absorptioncoefficient obtained by CPM measurement, the Urbach energy which is aslope of an Urbach tail (thin dotted line) was 78.7 meV. The integralvalue of the absorption coefficient in the energy range was derived insuch a manner that the absorption coefficient (thin dotted line) of theUrbach tail was subtracted from the absorption coefficient derived fromCPM measurement in the energy range shown with a dashed-line circle inFIG. 37A (see FIG. 37B). As a result, the absorption coefficient of thissample was found to be 2.02×10⁻⁴ cm⁻¹.

From the above, it can be considered that the localized state of themultilayer film of Sample 13 is due to an impurity or a defect. Thus,the multilayer film was found to have extremely low density of statesdue to an impurity or a defect. That is, it can be found that thetransistor including the multilayer film has stable electricalcharacteristics.

Example 7

In this example, the concentration of silicon in a multilayer filmincluded in a transistor which is one embodiment of the presentinvention is described. Here, the results of evaluating the multilayerfilm by SIMS measurement are described.

First, samples which were measured by SIMS are described.

A 10-nm-thick oxide film 81 containing In or Ga was formed over asilicon wafer Si, a 10-nm-thick oxide semiconductor film 82 was formedover the oxide film 81 containing In or Ga, and a 10-nm-thick oxide film83 containing In or Ga was formed over the oxide semiconductor film 82;thus, the multilayer film was formed.

In this example, the oxide film 81 containing In or Ga is an oxide filmformed by a sputtering method using an In—Ga—Zn oxide (In:Ga:Zn=1:3:2[atomic ratio]) target. Note that the film was formed in such a mannerthat an argon gas of 30 sccm and an oxygen gas of 15 sccm were used as afilm formation gas, the pressure was set to be 0.4 Pa, the substratetemperature was set to be 200° C., and a DC power of 0.5 kW was applied.

The oxide semiconductor film 82 is an oxide semiconductor film formed bya sputtering method using an In—Ga—Zn oxide (In:Ga:Zn=1:1:1 [atomicratio]) target. Note that the film was formed in such a manner that anargon gas of 30 sccm and an oxygen gas of 15 sccm were used as a filmformation gas, the pressure was set to be 0.4 Pa, the substratetemperature was set to be 300° C., and a DC power of 0.5 kW was applied.

The oxide film 83 containing In or Ga is an oxide film formed by asputtering method using an In—Ga—Zn oxide (In:Ga:Zn=1:3:2 [atomicratio]) target. Note that the film was formed in such a manner that anargon gas of 30 sccm and an oxygen gas of 15 sccm were used as a filmformation gas, the pressure was set to be 0.4 Pa, the substratetemperature was set to be 200° C., and a DC power of 0.5 kW was applied.

A sample which was not subjected to heat treatment after the multilayerfilm was formed and a sample which was subjected to heat treatment at450° C. for 2 hours were prepared. The sample which was not subjected toheat treatment is referred to as Sample 14, and the sample which wassubjected to heat treatment is referred to as Sample 15.

As for Sample 14 and Sample 15, the Si concentration [atoms/cm³] in adepth direction was measured using a time-of-flight secondary ion massspectrometry (ToF-SIMS). In FIG. 38A, the Si concentration [atoms/cm³]which is converted from the secondary ion intensity of SiO₃ in a depthdirection of the multilayer film in Sample 14 is shown, and in FIG. 38B,the Si concentration [atoms/cm³] which is converted from the secondaryion intensity of SiO₃ in a depth direction of the multilayer film inSample 15 is shown.

From FIGS. 38A and 38B, it was found that the Si concentration is highat the interface between the silicon wafer and the oxide film 81containing In or Ga and on the top surface of the oxide film 83containing In or Ga. Moreover, it was found that the Si concentration ofthe oxide semiconductor film 82 is about 1×10¹⁸ atoms/cm³, the lowerlimit of detection in Tof-SIMS. This is probably because, by providingthe oxide film 81 containing In or Ga and the oxide film 83 containingIn or Ga, the oxide semiconductor film 82 is not affected by siliconwhich is due to the silicon wafer, surface contamination, or the like.

Further, from the results shown in FIGS. 38A and 38B, it can be seenthat silicon is less likely to be diffused by the heat treatment, thoughentry of silicon mainly occurs at the time of film formation.

Thus, with the use of a multilayer film as described in this example, atransistor having stable electrical characteristics can be manufactured.

Reference Example

Here, the energy barrier between a source and a drain of a transistorincluding an oxide semiconductor is described.

In the case where an intrinsic or substantially intrinsic oxidesemiconductor film is used as an oxide semiconductor film which is to bea channel region, a barrier which is about half the energy gap of theoxide semiconductor film might be formed between the oxide semiconductorfilm and the pair of electrodes serving as a source electrode and adrain electrode in a transistor including the oxide semiconductor film.However, in practice, drain current starts flowing at a gate voltage ofabout 0 V in the Vg-Id characteristics of the transistor including theoxide semiconductor film, which suggests that there is a problem in theaforementioned idea.

Thus, as shown in FIG. 39A, a transistor with a structure including agate insulating film GI, an oxide semiconductor film OS over the gateinsulating film GI, and a source electrode S and a drain electrode Dprovided over the oxide semiconductor film OS was assumed, and the bandstructure of the transistor along dashed-dotted line H1-H2, in which thechannel length (L) was varied, was derived from calculation. Note thatin FIG. 39A, n-type low-resistance regions n are provided in regions ofthe oxide semiconductor film OS in contact with the source electrode Sand the drain electrode D. That is, the oxide semiconductor film OSincludes the low-resistance regions n and an intrinsic or substantiallyintrinsic region i. Note that in the calculation, the oxidesemiconductor film OS was assumed to have a thickness of 35 nm and thegate insulating film GI was assumed to have a thickness of 400 nm toperform the calculation.

The width of band bending was estimated by solving Poisson's equation,whereby the width of band bending was found to be a length characterizedby a Debye shielding length λ_(D). Note that in the following equation,k_(B) represents a Boltzmann constant.

$\begin{matrix}{\lambda_{D} = \sqrt{\frac{{ɛɛ}_{0}k_{B}T}{e^{2}{ni}}}} & \left\lbrack {{Formula}\mspace{14mu} 2} \right\rbrack\end{matrix}$

In the above equation, when the intrinsic carrier density ni of theoxide semiconductor film OS was 6.6×10⁻⁹ cm³, the relative permittivity∈ of the oxide semiconductor film OS was 15, and the temperature was 300K, the Debye shielding length λ_(D) was determined to be 5.7×10¹⁰ μm,which was an extremely large value. Thus, it can be found that theenergy barrier between the low-resistance region n and the intrinsic orsubstantially intrinsic region i is half the energy gap of the oxidesemiconductor film OS in the case where the channel length is longerthan 1.14×10¹¹ μm which is twice the Debye shielding length λ_(D).

FIG. 40 shows the results of calculation of band structures where thechannel lengths are 0.03 μm, 0.3 μm, 1 μm, 10 μm, 100 μm, and 1×10¹² μm.Note that the potentials of the source electrode and the drain electrodeare fixed to GND (0 V). Note that in FIG. 40, “n” represents thelow-resistance region, “i” represents the intrinsic or substantiallyintrinsic region interposed between the low-resistance regions, adashed-dotted line represents Fermi energy of the oxide semiconductorfilm, and a dashed line represents midgap of the oxide semiconductorfilm.

It was found from FIG. 40 that, in the case where the channel length is1×10¹² μm which is long enough, the difference in electron energybetween the low-resistance region and the intrinsic or substantiallyintrinsic region is half the energy gap of the oxide semiconductor film.However, it was found that, as the channel length is reduced, thedifference in electron energy between the low-resistance region and theintrinsic or substantially intrinsic region gradually becomes smallerand there is essentially no energy barrier when the channel length isshorter than or equal to 1 μm. Note that the electron energy of thelow-resistance region is fixed by the pair of electrodes serving as asource electrode and a drain electrode.

As described above, it can be determined that the energy barrier betweenthe low-resistance region and the intrinsic or substantially intrinsicregion is sufficiently low when the channel length is short.

Here, the reason why the energy barrier between the low-resistanceregion and the intrinsic or substantially intrinsic region issufficiently low when the channel length is short is considered.

Description is made on the schematic views of an oxide semiconductorfilm and the band structures of the oxide semiconductor film withreference to FIGS. 41A to 41C. In FIG. 41A, the conduction band bottomEc_0 of an oxide semiconductor film 600 including an intrinsic orsubstantially intrinsic region 601 and low-resistance regions 602 and603 is shown. Further, the channel length of the oxide semiconductorfilm 600 is denoted by L_0. In FIG. 41A, L_0>2λ_(D) is satisfied.

FIG. 41B shows an oxide semiconductor film whose channel length isshorter than that in FIG. 41A, and the band structure thereof. In FIG.41B, the conduction band bottom Ec_1 of an oxide semiconductor film 610including an intrinsic or substantially intrinsic region 611 andlow-resistance regions 612 and 613 is shown. Further, the channel lengthof the oxide semiconductor film 610 is denoted by L_1. In FIG. 41B, thechannel length of L_1<L_0 and L_1<2λ_(D) is satisfied.

FIG. 41C shows an oxide semiconductor film whose channel length isshorter than the oxide semiconductor films shown in FIGS. 41A and 41B,and the band structure thereof. In FIG. 41C, the conduction band bottomEc_2 of an oxide semiconductor film 620 including an intrinsic orsubstantially intrinsic region 621 and low-resistance regions 622 and623 is shown. Further, the channel length of the oxide semiconductorfilm 620 is denoted by L_2. The channel length of L_2<L_1 andL_2>>2λ_(D) is satisfied.

The energy difference between the Fermi level Ef and the conduction bandbottom Ec_0 is denoted by ΔH_0 in FIG. 41A, the energy gap between theFermi level Ef and the conduction band bottom Ec_1 is denoted by ΔH_1 inFIG. 41B, and the energy gap between the Fermi level Ef and theconduction band bottom Ec_2 is denoted by ΔH_2 in FIG. 41C.

In the oxide semiconductor film, regions in contact with the pair ofelectrodes serve as the low-resistance regions. Thus, the closer thejunction regions between the intrinsic or substantially intrinsic regionand the low-resistance regions are, the more lowered in energy and morebent the conduction band bottom is. In the case where the channel lengthL_0 is long enough as shown in FIG. 41A, the energy barrier ΔH_0corresponds to Eg(bandgap)/2.

On the other hand, when the channel length is reduced as shown in eachof FIGS. 41B and 41C, the bent portions of the conduction band bottom(Ec_1, Ec_2) overlap with each other; thus, it is probable that theenergy barriers ΔH_1 and ΔH_2 are lower than Eg/2. The phenomenon inwhich the conduction band bottom in the intrinsic or substantiallyintrinsic region is thus lowered by the reduction of the channel lengthis referred to as a conduction band lowering (CBL) effect in thisspecification.

Next, a bottom-gate transistor including a gate electrode GE providedunder the gate insulating film GI in the structure shown in FIG. 39A wasassumed, and the band structure of the transistor along dashed-dottedline H1-H2, in which the channel length (L) was varied, was derived fromcalculation. The structure of the transistor used in the calculation isshown in FIG. 39B. Note that in the calculation, the oxide semiconductorfilm OS was assumed to have a thickness of 35 nm and the gate insulatingfilm GI was assumed to have a thickness of 400 nm to perform thecalculation.

FIG. 42 shows the results of calculation of band structures where thechannel lengths are 1 μm, 10 μm, 50 μm, 100 μm, 1×10⁵ μm, and 1×10¹² μm.Note that the potentials of the source electrode, the drain electrodeand the gate electrode are fixed to GND (0 V). Note that in FIG. 42, “n”represents the low-resistance region, “i” represents the intrinsic orsubstantially intrinsic region interposed between the low-resistanceregions, a dashed-dotted line represents Fermi energy of the oxidesemiconductor film, and a dashed line represents midgap of the oxidesemiconductor film.

The band structures shown in FIG. 42 are the results obtained byperforming calculation in a manner similar to that in the structureshown in FIG. 39A. However, it can be found that, in the case where thegate electrode is provided as in the structure of FIG. 39B, the value ofthe energy barrier between the low-resistance region and the intrinsicor substantially intrinsic region does not depend on the channel length(L) and is substantially constant even when the channel length (L) islonger than 1 μm.

In FIG. 43, the height of the energy barrier with respect to the channellength (L) in each of the structures of FIG. 39A and FIG. 39B is shown.

From FIG. 43, it can be seen that the height of the energy barrier inthe structure of FIG. 39A without a gate electrode monotonicallyincreases as the channel length increases and becomes half the energygap of the oxide semiconductor film (i.e., 1.6 eV) when the channellength is 1×10¹² μm. On the other hand, it can be seen that the heightof the energy barrier of the structure of FIG. 39B with the gateelectrode does not depend on the channel length even when the channellength is longer than 1 μm.

From the above, since the energy barrier is lower than the value whichis half the energy gap of the oxide semiconductor film by the CBL effectin the transistor including the intrinsic or substantially intrinsicoxide semiconductor film, it can be considered that drain current startsflowing at a gate voltage of about 0 V in the Vg-Id characteristics.Further, since the value of the energy barrier of the transistor whosechannel length is longer than a certain length (1 μm) is constantwithout depending on the channel length, it can be considered that draincurrent starts flowing at a gate voltage of about 0 V in the Vg-Idcharacteristics in the transistor including the intrinsic orsubstantially intrinsic oxide semiconductor film.

The multilayer film included in the transistor of one embodiment of thepresent invention includes the intrinsic or substantially intrinsicoxide semiconductor film. Thus, it can be considered that, in thetransistor including the multilayer film, drain current starts flowingat a gate voltage of about 0 V in the Vg-Id characteristics.

Example 8

In this example, the results of manufacturing and evaluating displaydevices each including an organic EL element and a transistor fordriving the organic EL element are described.

The display devices manufactured in this example are Samples a (fourtypes: Sample 16, Sample 17, Sample 18, and Sample 19) in each of whicha transistor which is one embodiment of the present invention is used asthe transistor for driving the organic EL element, and Comparisonsamples b (four types: Comparison sample 1, Comparison sample 2,Comparison sample 3, and Comparison sample 4) which are comparativeexamples.

First of all, a process for manufacturing Sample a is described. In thisexample, the process is described with reference to FIGS. 4A to 4D.

First, as shown in FIG. 4A, a glass substrate was used as the substrate11, and the gate electrode 15 was formed over the substrate 11.

A 200-nm-thick tungsten film was formed by a sputtering method, a maskwas formed over the tungsten film by a photolithography process, andpart of the tungsten film was etched with the use of the mask, so thatthe gate electrode 15 was formed.

Next, the gate insulating film 17 was formed over the gate electrode 15.The structure and the manufacturing method of the gate insulating film17 are similar to those in Example 1; thus, they are omitted here.

Next, the multilayer film 20 was formed to overlap with the gateelectrode 15 with the gate insulating film 17 interposed therebetween.The structure and the manufacturing method of the multilayer film 20 aresimilar to those in Example 1 except that the substrate temperature atthe time of forming the oxide film containing In or Ga is set to 100°C.; thus, they are omitted here. The structure obtained through thesteps up to here is illustrated in FIG. 4B. Note that, in the transistorfor driving the organic EL element, a channel length was 11 μm and achannel width was 4 μm.

Next, after the gate electrode was exposed by partly etching the gateinsulating film 17 (this step is not illustrated), the pair ofelectrodes 21 and 22 in contact with the multilayer film 20 was formedas illustrated in FIG. 4C. The structure and the manufacturing method ofthe pair of electrodes 21 and 22 are similar to those in Example 1;thus, they are omitted here.

Next, a surface of the multilayer film 20 was subjected to cleaningtreatment using a phosphoric acid solution in which 85% phosphoric acidwas diluted by 100 times.

Next, the protective film 26 was formed over the multilayer film 20 andthe pair of electrodes 21 and 22 (see FIG. 4D). The structure and themanufacturing method of the protective film 26 are similar to those inExample 1; thus, they are omitted here.

Next, although not illustrated, an opening which exposes part of thepair of electrodes 21 and 22 was formed by partly etching the protectivefilm 26.

Next, a planarization film was formed (this and subsequent componentsare not shown) over the protective film 26. Here, the protective film 26was coated with a composition, and exposure and development wereperformed, so that a planarization film having an opening through whichthe pair of electrodes is partly exposed was formed. Note that as theplanarization film, a 2.0-μm-thick acrylic resin was formed. Then, heattreatment was performed. The heat treatment was performed at atemperature of 250° C. in an atmosphere containing nitrogen for onehour.

Next, a conductive film connected to part of the pair of electrodes wasformed. Here, for the lower electrode of the light-emitting element, a50-nm-thick titanium film, a 200-nm-thick aluminum film, and an8-nm-thick titanium film were formed by a sputtering method, andfurthermore, an indium tin oxide containing silicon oxide (ITSO) filmwas formed as a microcavity structure. The thickness of the ITSO filmsof light-emitting elements in a red pixel, a green pixel, and a bluepixel were 82 nm, 45 nm, and 5 nm, respectively.

Then, a partition wall was formed to cover an end portion of theconductive film. Here, a 1.0-μm-thick polyimide resin was formed as thepartition wall. Then, heat treatment was performed. The heat treatmentwas performed at a temperature of 250° C. in an atmosphere containingnitrogen for one hour.

Next, a spacer with an inverse tapered shape was formed on the partitionwall. Here, a 1.0-μm-thick spacer was formed with the use of a negativephotosensitive resin. Then, heat treatment was performed. The heattreatment was performed at a temperature of 250° C. in an atmospherecontaining nitrogen for one hour.

Further, heat treatment was performed at 230° C. in an atmospherecontaining nitrogen for one hour.

Next, an EL layer and an upper electrode were formed over the conductivefilm. All the light-emitting elements in different color pixels have thesame structures of the EL layer and the upper electrode. Thelight-emitting element of this example is a tandem light-emittingelement in which the EL layer includes a fluorescence-emitting unitincluding a blue light-emitting layer and a phosphorescence-emittingunit including a green light-emitting layer and a red light-emittinglayer. As the upper electrode, a 15-nm-thick film was formed byco-evaporation of magnesium and silver.

Here, in each of Sample 16, Sample 17, and Sample 18, a glass substratehaving a color filter and a black matrix was used as a countersubstrate. Further, in Sample 19, a glass substrate having a dryingagent containing calcium oxide in its recessed portion was used as acounter substrate.

Then, an ultraviolet curable resin (XNR5516Z manufactured by NagaseChemteX Co., Ltd.) was applied, as a sealant, to the counter substrate.

Next, the substrate 11 and the counter substrate were bonded withpressure applied.

Then, the sealant was cured by irradiation with ultraviolet light.Further, heat treatment was performed at 80° C. for one hour in a cleanoven.

Through the above process, Sample a was manufactured.

Further, a sample in which the oxide film 19 containing In or Ga inSample a was not formed was manufactured as Comparison sample b. Notethat, in each of Comparison sample 1, Comparison sample 2, andComparison sample 3, a glass substrate having a color filter and a blackmatrix was used as a counter substrate. In Comparison sample 4, a glasssubstrate having a drying agent containing calcium oxide in its recessedportion was used as a counter substrate.

In each of Sample a and Comparison sample b which were manufactured inthis example, the number of stages of a gate driver is 960 and thenumber of stages of a source driver is 1620 (RGB×540) as shown in FIG.44.

As for Sample a and Comparison sample b, current flowing in the drivingtransistor in each pixel when white light was emitted from an entirearea was measured. As shown in FIG. 44, current was measured from thecurrent monitoring side to the display signal side in a specific stageof the source driver.

In conditions of the measurement, an anode was set at 10 V and a cathodewas set at −4 V. Further, data voltage was set so that luminance wasequivalent to 300 cd/m², equivalent to 150 cd/m², or equivalent to 90cd/m² in Sample 16 and Sample 17 and Comparison sample 1 and Comparisonsample 2 and so that luminance was equivalent to 300 cd/m² or equivalentto 50 cd/m² in Sample 18 and Comparison sample 3. Data voltage of Sample19 and Comparison sample 4 was set so that luminance was equivalent to300 cd/m² or equivalent to 50 cd/m² in the case where the countersubstrate is similar to those of other samples. Specifically, first, ineach of other samples of which data voltage was set so that luminancewas equivalent to 300 cd/m² or equivalent to 50 cd/m², current flowingin the light-emitting element was measured. Then, in each of Sample 19and Comparison sample 4, data voltage was set so that current flowing inthe light-emitting element had a similar value.

Specifically, three values of 3.99 V, 2.85 V, and 2.41 V were used forSample 16; three values of 3.57 V, 2.68 V, and 2.03 V, for Sample 17;two values of 3.78 V and 1.91 V, for Sample 18; and two values of 3.78 Vand 1.98 V, for Sample 19. Further, three values of 3.67 V, 2.74 V, and2.20 V were used for Comparison sample 1; three values of 3.46 V, 2.57V, and 2.10 V, for Comparison sample 2; two values of 3.78 V and 1.98 V,for Comparison sample 3; and two values of 3.99 V and 2.41 V, forComparison sample 4.

In FIG. 45, the results of measuring currents of Sample 17 andComparison sample 2 are shown. The horizontal axis indicates the numberof stages of the gate driver and the vertical axis indicates current inFIG. 45. Here, the results of measuring current of the drivingtransistor in each pixel in a 1st stage, a 270th stage, a 540th stage,an 810th stage, an 811th stage, a 1080th stage, a 1350th stage, and a1620th stage of the source driver are shown together in one graph.

Further, in FIG. 46, variation in the difference of current betweenadjacent pixels in each sample is shown. The vertical axis indicates±3σ(row)/ave in FIG. 46. Here, σ(row) represents the standard deviationof the difference of current between adjacent pixels in a gate driver(row) direction, and ave represents the overall average value of a pixelcurrent.

From FIGS. 45 and 46, it can be seen that Sample a and Comparison sampleb each have small variation in current among pixels. In particular,Sample a including a transistor which is one embodiment of the presentinvention has smaller variation in current among pixels than Comparisonsample b. From the above, it has been shown that the electricalcharacteristics of the transistor can be improved in accordance with oneembodiment of the present invention. Further, it has been shown that theinitial display quality of the display device can be improved inaccordance with one embodiment of the present invention.

Further, an image of a checkered pattern of black and white wasdisplayed on the entire area of each of Sample 19 and Comparison sample4 for 72 hours. Data voltage at this time was set by a method similar tothat described above so that luminance was equivalent to 300 cd/m².

Then, current flowing in the driving transistor in each pixel when awhite image was displayed on the entire area of each of Sample 19 andComparison sample 4 was measured. In FIG. 47, the results of the displayon Sample 19 and Comparison sample 4 are shown. In FIGS. 48 to 51, theresults of measuring currents of Sample 19 and Comparison sample 4 areshown.

Data voltage at this time was set by a method similar to that describedabove so that luminance was equivalent to 50 cd/m² or equivalent to 300cd/m². The results of measuring current of Sample 19 in the case whereluminance was equivalent to 50 cd/m² are shown in FIG. 48, and theresults of measuring current of Comparison sample 4 in that case areshown in FIG. 49. The results of measuring current of Sample 19 in thecase where luminance was equivalent to 300 cd/m² are shown in FIG. 50,and the results of measuring current of Comparison sample 4 in that caseare shown in FIG. 51.

In FIGS. 48 to 51, the horizontal axis indicates the number of stages ofthe gate driver and the vertical axis indicates current. Here, theresults of measuring current of the driving transistor in each pixel ina 1st stage, an 810th stage, and a 1620th stage of the source driver areshown.

In each of Sample 19 and Comparison sample 4, an image like the oneobtained by reversing the image of the previously displayed checkeredpattern of black and white was observed at the time of displaying thewhite image on the entire area. This is probably because thecharacteristics of the driving transistor in a pixel located in a whiteportion of the checkered pattern were shifted in the positive directionwhile the image of the checkered pattern was displayed, and current wasreduced, leading to a decrease in luminance. Therefore, when white lightwas emitted from the entire area after that, the pixel which had beenlocated in the white portion of the checkered pattern probably decreasedin luminance as compared to the pixel which had been located in a blackportion of the checkered pattern, and thus, burning-in (or imageretention) of the image of the checkered pattern seemed to occur.

The above-described burn-in (decrease of current) in Sample 19 includinga transistor which is one embodiment of the present invention wasreduced as compared to that in Comparison sample 4. From the above, itwas shown that the electrical characteristics of the transistor can beimproved in accordance with one embodiment of the present invention.

A constant-current stress test was performed on a transistor(hereinafter, referred to as Transistor a) which is one embodiment ofthe present invention and was used for Sample a and a transistor(hereinafter, referred to as Transistor b) which was used for Comparisonsample b. The constant-current stress test was performed under an airatmosphere in a dark state (dark).

Note that the measurement of Vg-Id characteristics was performed bymeasuring drain current when drain voltage was set to 0.1 V or 10 V andgate voltage was swept in the range of −15 V to 15 V.

In the constant-current stress test, first, a substrate temperature wasset to room temperature (20° C. to 25° C.) to perform a firstmeasurement of Vg-Id characteristics. Then, as for Transistor a, thesubstrate temperature was set to 60° C., a source potential was set to aground potential (GND), a drain potential was set to 10 V, and a gatepotential was set to 6.11 V, and the state was maintained for 11 hours.As for Transistor b, the substrate temperature was set to 60° C., thesource potential was set to the ground potential (GND), the drainpotential was set to 10 V, and the gate potential was set to 5.63 V, andthe state was maintained for 13 hours. Note that the stress applicationwas stopped after a lapse of 100 seconds, a lapse of 300 seconds, alapse of 600 seconds, a lapse of 1000 seconds, a lapse of 1800 seconds,a lapse of 3600 seconds, a lapse of 7200 seconds, a lapse of 10000seconds, a lapse of 18000 seconds, a lapse of 21600 seconds, a lapse of25200 seconds, a lapse of 28800 seconds, a lapse of 32400 seconds, alapse of 36000 seconds, and a lapse of 39600 seconds (as for Transistora, also after a lapse of 43200 seconds and a lapse of 46800 seconds)from the start of the constant-current stress test, and the Vg-Idcharacteristics after each stress time were measured at roomtemperature.

In FIG. 52, the results of the constant-current stress test ofTransistor a and Transistor b are shown. The vertical axis indicates thepercentage of change in drain current and the horizontal axis indicatesstress time in FIG. 52. From FIG. 52, it can be seen that the change indrain current of Transistor a is smaller than that of Transistor b. Alsofrom the above, it has been shown that the electrical characteristics ofa transistor can be improved in accordance with one embodiment of thepresent invention.

Example 9

In this example, the results of measuring the concentration of animpurity in the oxide insulating film formed over the oxidesemiconductor film are described.

First of all, a manufacturing process of a transistor included in eachof Sample 20 to Sample 22 is described. In this example, the process isdescribed with reference to FIGS. 4A to 4D.

First, a glass substrate was used as the substrate 11, and the gateelectrode 15 was formed over the substrate 11.

A 100-nm-thick tungsten film was formed by a sputtering method, a maskwas formed over the tungsten film by a photolithography process, andpart of the tungsten film was etched with the use of the mask, so thatthe gate electrode 15 was formed.

Next, the gate insulating film 17 was formed over the gate electrode 15.

A 50-nm-thick silicon nitride film and a 200-nm-thick silicon oxynitridefilm were stacked as the gate insulating film 17.

The silicon nitride film was formed under the following conditions:silane with a flow rate of 50 sccm and nitrogen with a flow rate of 5000sccm were supplied as source gases to a treatment chamber of a plasmaCVD apparatus, the pressure in the treatment chamber was controlled to60 Pa, and the power of 150 W was supplied with the use of a 27.12 MHzhigh-frequency power source.

The silicon oxynitride film was formed under the following conditions:silane with a flow rate of 20 sccm and dinitrogen monoxide with a flowrate of 3000 sccm were supplied as source gases to a treatment chamberof the plasma CVD apparatus, the pressure in the treatment chamber wascontrolled to 40 Pa, and the power of 100 W was supplied with the use ofa 27.12 MHz high-frequency power source.

Note that each of the silicon nitride film and the silicon oxynitridefilm was formed at a substrate temperature of 350° C.

Next, the oxide semiconductor film was formed to overlap with the gateelectrode 15 with the gate insulating film 17 provided therebetween.Note that in this example, the oxide semiconductor film 18 of a singlelayer was formed instead of the multilayer film 20 shown in FIG. 4B.

Here, an IGZO film which was a CAAC-OS film was formed over the gateinsulating film 17 by a sputtering method, a mask is formed over theIGZO film by a photolithography process, and the IGZO film was partlyetched using the mask. Then, the etched IGZO film was subjected to heattreatment, so that the oxide semiconductor film 18 was formed. Note thatthe IGZO film formed in this example had a thickness of 35 nm.

The IGZO film was formed under the following conditions: a sputteringtarget where In:Ga:Zn=1:1:1 (atomic ratio) was used, argon with a flowrate of 50 sccm and oxygen with a flow rate of 50 sccm were supplied assputtering gases to a treatment chamber of a sputtering apparatus, thepressure in the treatment chamber was controlled to be 0.6 Pa, and thedirect current power of 5 kW was supplied. Note that the IGZO film wasformed at a substrate temperature of 170° C.

As the heat treatment, heat treatment was performed at 450° C. under anitrogen atmosphere for one hour, and then, heat treatment was performedat 450° C. under an atmosphere of nitrogen and oxygen for one hour.

Next, after the gate electrode was exposed by partly etching the gateinsulating film 17 (not illustrated), the pair of electrodes 21 and 22in contact with the oxide semiconductor film 18 was formed asillustrated in FIG. 4C.

Here, a conductive film was formed over the gate insulating film 17 andthe oxide semiconductor film 18, a mask was formed over the conductivefilm by a photolithography process, and the conductive film was partlyetched using the mask, so that the pair of electrodes 21 and 22 wasformed. Note that as the conductive film, a 400-nm-thick aluminum filmwas formed over a 50-nm-thick tungsten film, and a 100-nm-thick titaniumfilm was formed over the aluminum film.

Next, the oxide insulating film 23 was formed over the oxidesemiconductor film 18 and the pair of electrodes 21 and 22.

As the oxide insulating film 23, a silicon oxynitride film was formed bya plasma CVD method under the following conditions: silane with a flowrate of 30 sccm and dinitrogen monoxide with a flow rate of 4000 sccmwere used as source gases, the pressure in a treatment chamber was 40Pa, the substrate temperature was 220° C., and a high-frequency power of150 W was supplied to an upper electrode of parallel plate electrodes.

Next, the oxide insulating film 24 was successively formed over theoxide insulating film 23. Here, “successively” means that, after theoxide insulating film 23 was formed, the oxide insulating film 24 wasformed in the same plasma CVD apparatus without exposure to the air.

As the oxide insulating film 24, a 400-nm-thick silicon oxynitride filmwas formed by a plasma CVD method under the following conditions: silanewith a flow rate of 160 sccm and dinitrogen monoxide with a flow rate of4000 sccm were used as source gases, the pressure in a treatment chamberwas 200 Pa, the substrate temperature was 220° C., and a high-frequencypower of 1500 W was supplied to an upper electrode of parallel plateelectrodes. Under the above conditions, it is possible to form a siliconoxynitride film containing more oxygen than that in the stoichiometriccomposition. In other words, a silicon oxynitride film from which partof oxygen is released by heating can be formed.

Next, heat treatment was performed. The heat treatment was performed at350° C. in an atmosphere containing oxygen and nitrogen for one hour.

Through the above process, Sample 20 including a transistor was formed.

Note that Sample 21 was manufactured under conditions where the oxideinsulating film 23 was not formed in the manufacturing process of Sample20.

Further, a sample in which the film formation temperature of the oxideinsulating film 24 was set to 350° C. and the oxide insulating film 23and the oxide insulating film 24 were formed in different plasma CVDapparatuses in the manufacturing process of Sample 20 is referred to asSample 22. That is, Sample 22 was exposed to the air after the oxideinsulating film 23 was formed.

Next, Sample 20 to Sample 22 were measured by SIMS. FIG. 53A, FIG. 53B,and FIG. 53C show the concentration of hydrogen, the concentration ofnitrogen, and the concentration of fluorine, respectively, in the oxideinsulating film 23 and the oxide insulating film 24 in Sample 20.Further, FIG. 53D, FIG. 53E, and FIG. 53F show the concentration ofhydrogen, the concentration of nitrogen, and the concentration offluorine, respectively, in the oxide insulating film 24 in Sample 21.Furthermore, FIG. 54A shows the concentration of boron in the oxideinsulating film 23 and the oxide insulating film 24 in Sample 22, andFIG. 54B shows the concentration of boron in the oxide insulating film24 in Sample 21. In each of FIGS. 53A to 53F and FIGS. 54A and 54B, thehorizontal axis indicates the depth from the surface of each sample andthe vertical axis indicates the concentration of each element.

In Sample 20, the concentration of hydrogen and the concentration ofnitrogen are not changed at the interface between the oxide insulatingfilm 23 and the oxide insulating film 24. On the other hand, theconcentration of fluorine has a peak at the interface between the oxideinsulating film 23 and the oxide insulating film 24. From the followingdescription, the concentration of fluorine has a peak at the aboveinterface. After the oxide insulating film 23 was formed, the power of aplasma CVD apparatus was cut. Next, after the flow rate of a source gasintroduced into a treatment chamber and the pressure in the treatmentchamber were changed, power was resupplied to the plasma CVD apparatusto form the oxide insulating film 24. After the oxide insulating film 23was formed, the surface of the oxide insulating film 23 was exposed tothe atmosphere in the treatment chamber until the oxide insulating film24 was formed.

On the inner wall of the treatment chamber, fluorine or NF₃ which wasused in cleaning of the treatment chamber was attached, and the fluorineor NF₃ released from the inner wall of the treatment chamber wasattached to the surface of the oxide insulating film 23 while the oxideinsulating film 24 was formed just after the oxide insulating film 23was formed. Therefore, the concentration of fluorine is increased at theinterface between the oxide insulating film 23 and the oxide insulatingfilm 24 and thus has a peak.

Note that since only a single layer of the oxide insulating film 24 isprovided over the oxide semiconductor film 18 in Sample 21, theconcentration of fluorine in the oxide insulating film 24 does not havea peak as shown in FIG. 53F.

Further, as shown in FIGS. 54A and 54B, the concentration of boron has apeak at the interface between the oxide semiconductor film 18 and theoxide insulating film 23 and at the interface between the oxideinsulating film 23 and the oxide insulating film 24 in Sample 22. On theother hand, the concentration of boron has a peak at the interfacebetween the oxide semiconductor film 18 and the oxide insulating film 24in Sample 21. It is probable that boron released from a HEPA filter inan air conditioning apparatus is adsorbed to the sample when the sampleis exposed to an air atmosphere, resulting in the concentration havingsuch a peak. Thus, it can be determined that a plurality of insulatingfilms is stacked in different treatment chambers when a plurality ofpeaks in the concentration of boron is shown in the oxide semiconductorfilm and the oxide insulating films.

From the above, a state of stacking of oxide insulating films can beexamined by measuring an impurity concentration in the oxide insulatingfilms over the oxide semiconductor film by SIMS.

This application is based on Japanese Patent Application serial No.2012-234602 filed with Japan Patent Office on Oct. 24, 2012, JapanesePatent Application serial No. 2012-234606 filed with Japan Patent Officeon Oct. 24, 2012, Japanese Patent Application serial No. 2012-286826filed with Japan Patent Office on Dec. 28, 2012, and Japanese PatentApplication serial No. 2013-051659 filed with Japan Patent Office onMar. 14, 2013, the entire contents of which are hereby incorporated byreference.

What is claimed is:
 1. A semiconductor device comprising a transistor, the semiconductor device comprising: a gate electrode over a substrate; a gate insulating film over the gate electrode; a multilayer film over the gate insulating film; a pair of electrodes in electrical contact with the multilayer film; a first oxide insulating film over the gate insulating film, the multilayer film, and the pair of electrodes; and a second oxide insulating film over the first oxide insulating film, wherein the multilayer film includes an oxide semiconductor film and an oxide film, wherein the first oxide insulating film is an oxide insulating film through which oxygen is permeated, wherein the second oxide insulating film is an oxide insulating film containing more oxygen than that in a stoichiometric composition, wherein a threshold voltage of the transistor changes in a negative direction or a positive direction, and an amount of change is less than or equal to 1.0 V, wherein each of the oxide semiconductor film and the oxide film is In-M-Zn oxide, wherein the M represents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf, and wherein a proportion of M atoms in the oxide film is higher than a proportion of M atoms in the oxide semiconductor film.
 2. The semiconductor device according to claim 1, wherein the oxide semiconductor film contains at least one of In and Ga.
 3. The semiconductor device according to claim 1, wherein a conduction band bottom of the oxide film is closer to a vacuum level than a conduction band bottom of the oxide semiconductor film is.
 4. The semiconductor device according to claim 3, wherein an energy difference between the conduction band bottom of the oxide film and the conduction band bottom of the oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 5. The semiconductor device according to claim 1, wherein an absorption coefficient of the multilayer film derived from a constant photocurrent method is lower than 1×10⁻³/cm in an energy range from 1.5 eV to 2.3 eV.
 6. The semiconductor device according to claim 1, wherein a concentration of silicon between the oxide semiconductor film and the oxide film is lower than 2×10¹⁸ atoms/cm³.
 7. The semiconductor device according to claim 1, wherein the semiconductor device is one selected from the group consisting of a television device, a computer, and a tablet terminal.
 8. A semiconductor device comprising: a gate electrode over a substrate; a gate insulating film over the gate electrode; a multilayer film over the gate insulating film; a pair of electrodes in electrical contact with the multilayer film; a first oxide insulating film over the gate insulating film, the multilayer film, and the pair of electrodes; and a second oxide insulating film over the first oxide insulating film, wherein the multilayer film includes an oxide semiconductor film and an oxide film, wherein the second oxide insulating film is an oxide insulating film containing more oxygen than that in a stoichiometric composition, wherein each of the oxide semiconductor film and the oxide film is In-M-Zn oxide, wherein the M represents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf, and wherein a proportion of M atoms in the oxide film is higher than a proportion of M atoms in the oxide semiconductor film.
 9. The semiconductor device according to claim 8, wherein the oxide semiconductor film contains at least one of In and Ga.
 10. The semiconductor device according to claim 8, wherein a conduction band bottom of the oxide film is closer to a vacuum level than a conduction band bottom of the oxide semiconductor film is.
 11. The semiconductor device according to claim 10, wherein an energy difference between the conduction band bottom of the oxide film and the conduction band bottom of the oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 12. The semiconductor device according to claim 8, wherein an absorption coefficient of the multilayer film derived from a constant photocurrent method is lower than 1×10⁻³/cm in an energy range from 1.5 eV to 2.3 eV.
 13. The semiconductor device according to claim 8, wherein a concentration of silicon between the oxide semiconductor film and the oxide film is lower than 2×10¹⁸ atoms/cm³.
 14. The semiconductor device according to claim 8, wherein the semiconductor device is one selected from the group consisting of a television device, a computer, and a tablet terminal.
 15. A semiconductor device comprising: a gate electrode over a substrate; a gate insulating film over the gate electrode; a multilayer film over the gate insulating film; a pair of electrodes in electrical contact with the multilayer film; a first oxide insulating film over the gate insulating film, and the multilayer film; and a second oxide insulating film over the first oxide insulating film, wherein the multilayer film includes an oxide semiconductor film and an oxide film, wherein the second oxide insulating film is an oxide insulating film containing more oxygen than that in a stoichiometric composition, wherein each of the oxide semiconductor film and the oxide film is In-M-Zn oxide, wherein the M represents Al, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf, and wherein a proportion of M atoms in the oxide film is higher than a proportion of M atoms in the oxide semiconductor film.
 16. The semiconductor device according to claim 15, wherein the oxide semiconductor film contains at least one of In and Ga.
 17. The semiconductor device according to claim 15, wherein a conduction band bottom of the oxide film is closer to a vacuum level than a conduction band bottom of the oxide semiconductor film is.
 18. The semiconductor device according to claim 17, wherein an energy difference between the conduction band bottom of the oxide film and the conduction band bottom of the oxide semiconductor film is greater than or equal to 0.05 eV and less than or equal to 2 eV.
 19. The semiconductor device according to claim 15, wherein an absorption coefficient of the multilayer film derived from a constant photocurrent method is lower than 1×10⁻³ /cm in an energy range from 1.5 eV to 2.3 eV.
 20. The semiconductor device according to claim 15, wherein a concentration of silicon between the oxide semiconductor film and the oxide film is lower than 2×10¹⁸ atoms/cm³.
 21. The semiconductor device according to claim 15, wherein the semiconductor device is one selected from the group consisting of a television device, a computer, and a tablet terminal. 